Co-reporter:Jiage Jia, Yanjun Niu, Panpan Zhang, Dongdi Zhang, Pengtao Ma, Chao Zhang, Jingyang Niu, and Jingping Wang
Inorganic Chemistry September 5, 2017 Volume 56(Issue 17) pp:10131-10131
Publication Date(Web):August 16, 2017
DOI:10.1021/acs.inorgchem.7b01231
A monomeric tricobalt(II)-substituted phosphotungstate polyanion, [H9P2W15O62Co3]9–, is stabilized by the attachement of an organometallic group, {Mn(CO)3}, for the first time. The resulting polyoxometalate-supported [Mn(CO)3]+ complex (1) can be used as an efficient catalyst in the cycloaddition of CO2 with epoxides under mild reaction conditions with pyrrolidinium bromide as a cocatalyst. Besides, magnetic measurements show that the compound exhibits weaker ferromagnetic interactions at low temperature.
Co-reporter:Vikram Singh, Pengtao Ma, Michael G. B. Drew, Jingyang Niu, Jingping Wang, and Guo-Xin Jin
Inorganic Chemistry October 16, 2017 Volume 56(Issue 20) pp:12520-12520
Publication Date(Web):September 22, 2017
DOI:10.1021/acs.inorgchem.7b01819
Polyoxometalates (POMs), emerging as a new class of porous molecular materials, play a promising role in homo- and heterogeneous catalysis. Among them, noble-metal-decorated POMs have a profound impact as catalytic materials. Thus, it is imperative to design and structurally explore new catalysts including noble metals. Herein, two new clusters, H3[(Cp*Rh)4PMo8O32]·14H2O (1) and H5[Na2(Cp*Ir)4PMo8O34]·13H2O (2) (Cp* = pentamethylcyclopentadienyl), based on a heterooctamolybdate anionic core were successfully obtained via a one-pot reaction using [Cp*MCl2]2 [M = Rh (1) and Ir (2)] and Na2MoO4 in acidic conditions. Compounds 1 and 2 were well characterized in the solid state by single-crystal X-ray diffraction, IR, and thermogravimetric analysis and in solution by UV–vis, electrospray ionization mass spectrometry, and electrochemistry. Compounds 1 and 2 represent an important class of structurally isolated organometallic POM-based clusters that were successfully nanostructured onto Ni foam and electrochemically reduced after 48 h of electrolysis to M/MoO2, where M = Rh (3) and Ir (4), nanocomposite hybrid materials on a Ni foam surface in a 0.1 M KOH solution. The modified electrocatalysts (3 and 4) show efficient hydrogen evolution reaction activities almost comparable to those of high-grade Pt/C at 0.1 M KOH. The nanostructured POMs [1- and 2@NF (Ni foam)] and their corresponding reduced products (3 and 4) were observed by scanning electron microscopy, energy-dispersive X-ray spectroscopy, powder X-ray diffraction, and X-ray photoelectron spectroscopy and further proven by transmission electron microscopy (TEM) and high-resolution TEM.
Co-reporter:Yu Huo, Rong Wan, Pengtao Ma, Junliang Liu, Yancong Chen, Dandan Li, Jingyang Niu, Jingping Wang, and Ming-Liang Tong
Inorganic Chemistry November 6, 2017 Volume 56(Issue 21) pp:12687-12687
Publication Date(Web):October 24, 2017
DOI:10.1021/acs.inorgchem.7b02251
A novel dysprosium(III)-containing polytungstoarsenate, [{(AsW9O33)3Dy2(H2O)4W4O9(H2O)}2(NH2(CH2PO3)2)]33–, comprising two identical subunits bridged by an organophosphonate ligand shows single-molecule-magnet (SMM) behavior. Magnetic studies reveal that this complex exhibits a butterfly-shaped hysteresis loop up to 8 K, and a thermally activated energy barrier of 101(5) K reached a breakthrough among all polyoxometalate-supported SMMs.
Co-reporter:Ke Wang, Yanjun Niu, Dongyan Zhao, Yanxin Zhao, Pengtao Ma, Dongdi Zhang, Jingping Wang, and Jingyang Niu
Inorganic Chemistry November 20, 2017 Volume 56(Issue 22) pp:14053-14053
Publication Date(Web):November 2, 2017
DOI:10.1021/acs.inorgchem.7b02207
The high-nuclearity polyoxovanadate-based carboxylate derivative K6H[VV17VIV12(OH)4O60(OOC(CH2)4COO)8]·nH2O (1) has been successfully synthesized by conventional aqueous methods and structurally characterized. The [VV17VIV12(OH)4O60(OOC(CH2)4COO)8]7– polyanion is built up from three cages: one {VV17(OH)4O44} cage and two identical [(VIV3O6)2(OOC(CH2)4COO)4]8– cages. Of the three cages, the {VV17(OH)4O44} is a purely inorganic polyoxovanadate cluster, whereas each of the [(VIV3O6)2(OOC(CH2)4COO)4]8– cages is a vanadium-based organic–inorganic hybrid cluster framed via four adipate ligands linking simultaneously to two triangular {V3} units. The two [(VIV3O6)2(OOC(CH2)4COO)4]8– cages are covalently attached to the central {VV17(OH)4O44} cage via V–O–V bonds in a linear arrangement, resulting in a {V29}-based hybrid cluster skeleton. The catalytic properties of compound 1 for the oxidation of sulfides by tert-butyl hydroperoxide were investigated, and the result indicates that 1 exhibits excellent catalytic activity for the oxidation of sulfides under mild conditions.
Co-reporter:Dongdi Zhang, Zhijie Liang, Suyi Liu, Longsheng Li, Pengtao Ma, Shufang Zhao, Haiying Wang, Jingping Wang, and Jingyang Niu
Inorganic Chemistry May 15, 2017 Volume 56(Issue 10) pp:5537-5537
Publication Date(Web):May 3, 2017
DOI:10.1021/acs.inorgchem.6b02524
Polyoxometalates (POMs) of Nb and Ta are greatly different from those of Mo, W, and V that have been studied extensively and developed well. The latter can be formed simply by acidification of their aqueous monomeric oxoanions and has found application areas from catalysis to magnetism, materials science, medicine, and nanotechnology. Even now the polyoxoniobate (PONb) chemistry has accelerated dramatically over the last 15 years, and a vast expansion of available PONbs has been reported. However, after nearly 200 years of POM research, Ta-based POM chemistry is still at its infant stage and only dominated by the isopolyoxotantalate ions (Ta6 and Ta10) and transition-metal-capped Ta6 species, along with two Ti-substituted polyoxotantalates [Ti2Ta8O28]8– and [Ti12Ta6O44]10– reported very recently. In this study, we discover two novel peroxotantalophosphate clusters [P4(TaO2)6O25]12– (1) and [P4(TaO2)6O24]10– (2) by incorporating phosphorus heteroatom into Ta-oxo framework, which represent the first two examples of heteropolytantalate. Interestingly, two P2Ta3 half-units are cis- and trans-condensed in 1 and 2, leading to “open” and “closed” configurations, respectively. These two chemically and structurally related clusters can be isolated in a controlled manner, and the yields are relatively high. Both compounds were characterized in the solid state by single-crystal X-ray diffraction, 31P MAS NMR, FT-IR, TGA, and elemental analysis as well as by 31P NMR in solution. The results presented here provide a strategy to be applicable to other heteroatom-incorporated polyoxotantalates and further expand the phase space for polyoxotantalate chemistry.
Co-reporter:Jipeng Guo, Yaqing Zhao, Chao Zhang, Pengtao Ma, Dongdi Zhang, Jingyang Niu, Jingping Wang
Inorganic Chemistry Communications 2017 Volume 75() pp:5-7
Publication Date(Web):January 2017
DOI:10.1016/j.inoche.2016.11.010
•A new ring-shaped Cr-containing tungstophosphate•{P2W12} subunits are linked by {Cr(H2O)2} bridges into a ring shape.•ESI-MS analysis, electrochemistry behavior and magnetic propertyA new Cr-containing tungstophosphate [(Cr(H2O)2)3(H2P2W12O48)3]27 − (1a) was prepared via simple, one-pot reaction method, which was isolated as hydrated potassium salt, K4[H23(Cr(H2O)2)3(H2P2W12O48)3]·34H2O (1). Compound 1 was characterized by single-crystal X-ray diffraction, FT-IR, UV-vis, elemental analyses, thermal analysis, electrochemistry and electrospray ionization mass spectrometry. Polyoxoanion 1a is composed of three {P2W12} subunits linked by three {Cr(H2O)2} bridges alternately, forming a ring in a corner-sharing mode. Moreover, variable temperature magnetic susceptibility indicates that 1 shows antiferromagnetic behavior.A new Cr-containing trimeric tungstophosphate [(Cr(H2O)2)3(H2P2W12O48)3]27 − based on [H2P2W12O48]12 − building block has been prepared and characterized.
Co-reporter:Xiaopeng Sun, Ran Ban, Pengtao Ma, Jiawei Wang, Dongdi Zhang, Jingyang Niu, Jingping Wang
Synthetic Metals 2017 Volume 223() pp:19-25
Publication Date(Web):January 2017
DOI:10.1016/j.synthmet.2016.11.035
•Four structurally novel transition-metal-bridging risedronate-based polyoxomolybdates (PODs) were well established and characterized.•The face-sharing {MoO6} octahedra are employed and compound 4 is the first example containing isomeric polyanions 4a and 4b in organophosphonate-based PODs.•Magnetic investigations indicate that compounds 1 and 4 displays ferromagnetic and antiferromagnetic interactions, respectively.Four structurally novel transition-metal (TM)-bridging risedronate (Ris)-based polyoxomolybdates (Ris-based PODs), Cs4Na2[{MO(H2O)2}(Mo2O5L)]2·16H2O [M = Ni (1), Co (2)], Cs2Na2H[(CrO2){(Mo2O5)(HL)}2]·17H2O (3) Cs11Na4H7[MnO2{HL(Mo2O5)MnO2(H2O)(Mo2O4) L}2]2·26H2O (4) [L = {O3PC(O)(CH2-3-C5NH4)PO3}, HL = {O3PC(O)(CH2-3-C5NH5)PO3}], have been presented through conventional aqueous solution and characterized by single crystal X-ray diffraction and PXRD, SEM images and EDX analyses, IR and UV spectra, elemental analyses and X-ray photoelectron spectroscopy. Compared to the reported edge-sharing {MoV2O4}, the face-sharing building block {Mo2VIO5} is employed in compounds 1–4, which are uncommon in Ris-based PODs. Furthermore, preliminary variable-temperature magnetic susceptibility measurements indicate that 1 and 4 display weak ferromagnetic behaviors and antiferromagnetic interactions, respectively.The characterizations and the magnetic properties of the synthesized four structurally novel TM-bridging Ris-based PODs were well established in this paper.
Co-reporter:Shumin Chen;Pengtao Ma;Huihui Luo;Yangyang Wang;Jingyang Niu;Jingping Wang
Chemical Communications 2017 vol. 53(Issue 26) pp:3709-3712
Publication Date(Web):2017/03/28
DOI:10.1039/C7CC00591A
A europium-containing isopolyoxoniobate with the formula (CN3H6)7K3H17{Eu3(H2O)9Nb48O138(H2O)6}·40H2O is synthesized under the protection of citric acid. ESI-MS spectra show that the polyoxoanion structural unit {Eu3(H2O)9[Nb48O138(H2O)6]}27− is intact in aqueous solution. Moreover, its solid-state luminescence displays a red emission with the long lifetime of 258 μs.
Co-reporter:Ran Ban;Xiaopeng Sun;Jiawei Wang;Pengtao Ma;Chao Zhang;Jingyang Niu;Jingping Wang
Dalton Transactions 2017 vol. 46(Issue 18) pp:5856-5863
Publication Date(Web):2017/05/09
DOI:10.1039/C7DT00615B
Four structurally intriguing members of a new family of lanthanide (Ln)-containing organophosphonate-functionalized polyoxotungstates with the general formula K2[Ln(H2O)4(AsW9O33)(W2O3)(O3PCOHCH3PO3)Ln(H2O)7]2·15H2O [Ln = Ce (1Ce), Nd (2Nd), Sm (3Sm) and Eu (4Eu)] were directly isolated by controlling the reaction parameters and well established by single-crystal X-ray diffraction, PXRD analyses, IR spectra, elemental analyses, TG and EDX analyses. All the four three-dimensional frameworks consist of the S-shaped inorganic building block {[(AsW9O33)(W2O3)]2}, two organophosphonate groups {O3PCOHCH3PO3} and four Ln ions. The magnetic properties of the four compounds and the solid-state photoluminescence properties of 2Nd, 3Sm, and 4Eu were also fully investigated.
Co-reporter:Li Li;Yanjun Niu;Kaili Dong;Pengtao Ma;Chao Zhang;Jingyang Niu;Jingping Wang
RSC Advances (2011-Present) 2017 vol. 7(Issue 46) pp:28696-28701
Publication Date(Web):2017/05/30
DOI:10.1039/C7RA03254D
An organic–inorganic hybrid polyoxoniobate, Na8{Ni[Ni(en)]2Nb10O32}·28H2O (1) (en = ethanediamine), has been synthesized and characterized. It represents the first example of a trinuclear nickel-containing polyoxoniobate. The catalysis of 1 for allylic alcohol epoxidation was investigated at room temperature in aqueous solution, and was found to catalyze the epoxidation of 3-methyl-2-buten-1-ol with high conversion (98%) and selectivity (94%). Furthermore, magnetic measurements showed that the compound exhibits ferromagnetic interactions.
Co-reporter:Rong Wan;Pengtao Ma;Feng Hu;Dongdi Zhang;Chao Zhang
Journal of Cluster Science 2017 Volume 28( Issue 3) pp:1761-1771
Publication Date(Web):27 February 2017
DOI:10.1007/s10876-017-1184-2
Two magnetic 2D inorganic–organic hybrid phosphotungstates, K2(H2dap)4[Cu(dap)2]{Cu(A-α-PW9O34)2[Cu(dap)]2}·6H2O (1) and [Cu(dap)2]H2{Cu[Cu(dap)Cu(dap)2(A-α-PW9O34)]2[Cu(dap)]2}·4H2O (2) (dap = 1,3-diaminopropane) have been synthesized and well-characterized. Both 1 and 2 show a 2D layer-like framework with the (4, 4)-connected topological network based on 1D sinusoidal chain-like structure. The studies of magnetic properties indicate that 1 and 2 are indicative of a typical antiferromagnetic coupling between Cu2+ cations.
Co-reporter:Jin Wang, Pengtao Ma, Yaping Wang, Dongdi Zhang, Jingyang Niu, Jingping Wang
Journal of Physics and Chemistry of Solids 2017 Volume 110(Volume 110) pp:
Publication Date(Web):1 November 2017
DOI:10.1016/j.jpcs.2017.06.007
•The two compounds are dimers, in which the ligand of 1,3,5-tris(carboxymethoxy)benzene fully exhibited its flexibility.•After just 1 min of irradiation compound 2 can display a highly obvious color change.•The coloration speed of the two compounds is higher than polyoxomolybdates functionalized by other applied carboxylic acids.Two inorganic-organic hybridized polyoxomolybdates, Cs8NaH [(SeMo6O21)C6H3O3(CH2CO2)3]2·10H2O (1) and Cs8H4 [(AsMo6O21)C6H3O3(CH2CO2)3]2·10H2O (2), functionalized by a flexible tri-podal multicarboxylic ligand 1,3,5-tris (carboxymethoxy)benzene (TCMB) have been synthesized and characterized. Single-crystal X-ray diffraction analysis reveals that each of the two hybrids consists of two {XMo6} (X = Se, As) units supported by two TCMB molecules. The photochromism and thermochromism behaviors of the two compounds have been explored. The color of compound 2 could change dramatically from white to black within just 1 min of irradiation by a Xe lamp. During thermochromic experiments the two compounds change their color at 423 K for 1 and 393 K for 2, respectively.
Co-reporter:Haiying Wang;Lili Hou;Chen Li;Dongdi Zhang;Pengtao Ma;Jingping Wang;Jingyang Niu
RSC Advances (2011-Present) 2017 vol. 7(Issue 58) pp:36416-36420
Publication Date(Web):2017/07/20
DOI:10.1039/C7RA06291E
We present the second example of mixed Nb/W addendum based trimer, Cs12[(SiW9Nb3O38)3WO3(OH)3]·33H2O by utilizing in situ formed Keggin-type {SiW9(NbO2)3} unit as the secondary building block. The polyanion [(SiW9Nb3O38)3WO3(OH)3]12− incorporates three saturated niobium-substituted tungstosilicate {SiW9Nb3} clusters that are linked together by three Nb–O–Nb bridges and a tungsten joint. The compound has been thoroughly characterized by single crystal X-ray diffraction, UV-Vis spectroscopy, TG analysis, PXRD and FTIR spectra. In addition, the photocatalytic activities of the title compound and the two precursors A-α-Na10[SiW9O34]·23H2O and K7HNb6O19·13H2O for H2 evolution were also evaluated.
Co-reporter:Zhijie Liang;Ke Wang;Dongdi Zhang;Pengtao Ma;Jingyang Niu;Jingping Wang
Dalton Transactions 2017 vol. 46(Issue 5) pp:1368-1371
Publication Date(Web):2017/01/31
DOI:10.1039/C6DT04223F
A new heteropolyniobate, [Fe3Nb25O76]18−, persists in aqueous solution by means of electrospray ionization mass spectrometry. It has been synthesized and characterized by IR, TGA, EDX-SEM, magnetic and single-crystal X-ray diffraction, and it features an Fe-centred Nb-Keggin unit {Fe3Nb10}.
Co-reporter:Rong Wan;Pengtao Ma;Mengdan Han;Dongdi Zhang;Chao Zhang;Jingyang Niu;Jingping Wang
Dalton Transactions 2017 vol. 46(Issue 16) pp:5398-5405
Publication Date(Web):2017/04/19
DOI:10.1039/C7DT00250E
Two novel trans-isomers of 1 : 2-type lanthanide-containing monolacunary Dawson-type tungstophosphates [Ln(α2-P2W17O61)2]17− (Ln = LaIII (1), CeIII (2)) were successfully isolated and characterized by elemental analysis, IR, TG, and 31P NMR studies. Both polyanions 1 and 2 consist of one Ln3+ ion sanwiched between two monolacunary Dawson-type tungstophosphates fragments [α2-P2W17O61]10− oriented at 180° with respect to each other. The solid-state and solution 31P NMR spectroscopy revealed that the trans-[Ce(α2-P2W17O61)2]17− species probably quickly isomerizes to the cis-isomer species in solution.
Co-reporter:Jipeng Guo;Yanjun Niu;Lanying Song;Qiaofei Xu;Jingkun Lu;Pengtao Ma;Dongdi Zhang;Chao Zhang;Jingyang Niu;Jingping Wang
Dalton Transactions 2017 vol. 46(Issue 38) pp:12981-12987
Publication Date(Web):2017/10/03
DOI:10.1039/C7DT02471A
A series of new lanthanide-containing peroxoisopolyoxotungstates, K6Na4[H32{Ln4(WO4)(H2O)16[W7O22(O2)2]4}3]·105H2O [Ln = CeIII (1), NdIII (2), SmIII (3), TbIII (4), ErIII (5)], have been successfully synthesized and structurally characterized. All polyanions [LnIII4(WO4)(H2O)16{W7O22(O2)2}4]14− are isostructural and consist of a central [LnIII4(WO4)(H2O)16]10+ cluster surrounded by four peripheral [W7O22(O2)2]6− units. They could act as efficient recyclable catalysts for the epoxidation of various alkenes including different cycloalkenes, styrene derivatives, internal and long-chain alkenes. Under optimal conditions, catalyst 2 displays the best catalytic activity for the oxidation of cyclooctene with high cyclooctene conversion (98.3%) and excellent selectivity (up to 99%) and could be reused for three cycles with a negligible decrease in reactivity.
Co-reporter:Jin Wang;Yanfen Liang;Pengtao Ma;Dongdi Zhang;Jingyang Niu;Jingping Wang
CrystEngComm (1999-Present) 2017 vol. 19(Issue 2) pp:207-213
Publication Date(Web):2017/01/04
DOI:10.1039/C6CE02343F
Four inorganic–organic hybrids based on multicarboxylic acids and antimoniomolybdates, namely, (NH4)4(C3N2H5)4H4[(SbMo6O21)2{OOC(CH2)4COO}3]·7H2O (1), (NH4)8(C3N2H5)2H2[(SbMo6O21)2{OOC(CH2)6COO}3]·8H2O (2), (NH4)24[(SbMo6O21)4{C6H3(COO)3}4]·8H2O (3), and (NH4)6[(SbMo6O21){C9H9(COO)3}]·3H2O (4) have been synthesized under conventional solution conditions. Studies reveal that these compounds are monomers, dimers or tetramers, depending on the structures of the coordinated carboxylic acids. Also, the photochromic properties of these compounds were studied and compared, and based on the different carboxylic acids they displayed great disparities in the coloration speed under irradiation; the speed sequence is: 4 {benzene-1,3,5-triacetic acid (BTA)} > 2 (suberic acid) > 1 (adipic acid). It is indicated that compared to the applied aliphatic acids, the aromatic carboxylic acid ligands will facilitate the enhancement of the coloration speed of organic-POM hybrids.
Co-reporter:Shufang Zhao;Zhijie Liang;Qiaohua Geng;Pengtao Ma;Chao Zhang;Jingyang Niu;Jingping Wang
CrystEngComm (1999-Present) 2017 vol. 19(Issue 20) pp:2768-2774
Publication Date(Web):2017/05/22
DOI:10.1039/C7CE00603A
A novel phosphorus incorporated peroxopolyoxoniobate (CN3H6)6H4[P4Nb6(O2)6O24]·4H2O (1) has been successfully synthesized and characterized. Compound 1 possesses a cluster of [P4Nb6(O2)6O24]10− and can be viewed as the fusion of two {P2Nb3(O2)3O14} subunits by corner-sharing of bridging oxygen atoms. Furthermore, by reacting transition metals with the polyanion [P4Nb6(O2)6O24]10− formed in situ, we have discovered a series of transition-metal-containing niobium phosphate cluster derivatives, (CN3H6)4H4[{Cd(H2O)4}{P4Nb6(O2)6O24}]·7H2O (2), Cs3H3{[M(H2O)4.5]2[P4Nb6(O2)6O24]}·5H2O [M = Co (3), Ni (4), Zn (5)] and Cs3H3[{Cd(H2O)4}2{P4Nb6(O2)6O24}]·12H2O (6). Compounds 2–6 are based on the {P4Nb6(O2)6O24}10− cluster and 3, 4 and 5 show zero-dimensional constructions whereas 2 and 6 can form 1D chains attributed to the larger radius of Cd2+.
Co-reporter:Pengtao Ma, Feng Hu, Rong Wan, Yu Huo, Dongdi Zhang, Jingyang Niu and Jingping Wang
Journal of Materials Chemistry A 2016 vol. 4(Issue 23) pp:5424-5433
Publication Date(Web):06 May 2016
DOI:10.1039/C6TC00960C
A series of inorganic–organic hybrid double-tartaric bridging mono-lanthanide substituted phosphotungstates with a general formula of [N(CH3)4]6K3H7[Ln(C4H2O6)(α-PW11O39)]2·27H2O (Ln = Dy for 1Dy, Er for 2Er, and Yb for 3Yb) have been synthesized by the reactions of K14[P2W19O69(H2O)]·24H2O and LnCl3·6H2O in the presence of tartaric acid and tetramethyl ammonium counterions in an aqueous medium. Crystal structure analyses reveal that 1Dy–3Yb are isomorphic and are all built from two mono-lanthanide substituted Keggin polyoxoanion fragments joined together by two tartaric ligands. 1Dy–3Yb exhibit reversible photochromism and they can change from white (for 1Dy and 3Yb) or pink (for 2Er) to blue upon UV irradiation and then their colors gradually recover in the dark for about five days. The solid-state photoluminescence spectra of 1Dy–3Yb display their characteristic emissions of lanthanide components based on their 4f–4f transitions. Moreover, the fluorescence of 1Dy displays an effectively switchable behaviour when exposed to UV light, the intensity of the emission band at 573 nm gradually weakens as the irradiation time increases and the intensity drops to 2.4% of the original intensity after 30 minutes. It is noteworthy that the frequency dependence of the ac-susceptibility was found for 1Dy, suggesting a typical single-molecule magnet (SMM) behavior with an energy barrier of 20 K.
Co-reporter:Pengtao Ma; Rong Wan; Yueyan Wang; Feng Hu; Dongdi Zhang; Jingyang Niu;Jingping Wang
Inorganic Chemistry 2016 Volume 55(Issue 2) pp:918-924
Publication Date(Web):January 5, 2016
DOI:10.1021/acs.inorgchem.5b02473
It is challenging to explore and prepare high-nuclear lanthanide (Ln) cluster-encapsulated polyoxometalates (POMs). Herein, we fabricate an unprecedented Ce10-cluster-embedded polyoxotungstate (POT) (TMA)14H2[CeIII(H2O)6]{[CeIV7CeIII3O6(OH)6(CO3)(H2O)11][(P2W16O59)]3}·41H2O (1) (TMA = tetramethyleneamine) by coordination-driven self-assembly strategy, which contains the largest Ce cluster [CeIV7CeIII3O6(OH)6(CO3)(H2O)11] (Ce10) in all the Ln-containing POM chemistry to date. Self-assembly of the in situ dilacunary [P2W16O59]12– fragments and mixed Ce3+ and Ce4+ ions by means of coordination-driven force results in a novel 2D graphite-like framework constructed from mixed-valent cerium(III/IV) cluster {Ce10} encapsulated poly(POT) units and Ce3+ ions. The most remarkable feature is that the skeleton of the centrosymmetric Ce10-cluster-embedded POT trimer contains three dilacunary [P2W16O59]12– fragments trapping a novel {Ce10} cluster via 18 terminal-oxo and three μ4-oxo atoms.
Co-reporter:Jie Li, Jipeng Guo, Jiage Jia, Pengtao Ma, Dongdi Zhang, Jingping Wang and Jingyang Niu
Dalton Transactions 2016 vol. 45(Issue 15) pp:6726-6731
Publication Date(Web):01 Mar 2016
DOI:10.1039/C6DT00352D
A novel isopentatungstate-supported metal carbonyl derivative KH[(CH3)4N]3{[Re(CO)3]4[(μ2-OH)(μ3-O)(W5O18)]}·6H2O (1) has been synthesized and characterized. Compound 1 represents the second example of isopolyoxotungstate-supported metal carbonyl derivative. The catalysis of 1 for alkene epoxidation with H2O2 was investigated, and was found to efficiently catalyze the epoxidation of cyclooctene with high conversion (98.9%) and excellent selectivity (99%). Furthermore, the solution behavior of the polyanion 1 was also explored using electrospray ionization mass spectrometry.
Co-reporter:Feng Hu, Pengtao Ma, Mengdan Han, Rong Wan, Jingping Wang, Jingyang Niu
Inorganic Chemistry Communications 2016 Volume 67() pp:103-106
Publication Date(Web):May 2016
DOI:10.1016/j.inoche.2016.03.018
•New organic-inorganic hybrid tetrameric polyoxometalate•Four lacunary Dawson-type [α2-P2W17O61]10 − joined together by eight cerium cations•Eight isonicotinic acids as the organic pendants coordinating to cerium cationsA novel octa-nuclear cerium(III)-containing organic-inorganic hybrid polyoxometalate [N(CH3)4]8H16[{Ce(η1-C6H5NO2)2(H2O)6[Ce(H2O)3(α2-P2W17O61)]}{Ce(η2-C6H5NO2)2(H2O)5[Ce(H2O)(α2-P2W17O61)]}]2·90H2O (C6H5NO2 = isonicotinic acid) (1) was obtained, which had been hydrothermally synthesized and characterized by IR spectrum, thermogravimetric analysis (TGA), and X-ray single-crystal diffraction. Structural analysis indicated at 1 is composed of four lacunary Dawson-type units [α2-P2W17O61]10 − joined together by eight cerium cations forming an uncommon zigzag tetrameric structure with eight isonicotinic acids as the organic pendants coordinating to the cerium cations. Magnetic property studies indicate that obvious antiferromagnetic interactions exist in eight Ce3 + cations.A novel octa-nuclear cerium(III)-containing organic-inorganic hybrid tetrameric polyoxometalate based on monovacant Dawson-type units [α2-P2W17O61]10 − with eight isonicotinic acids as pendants has been synthesized and characterized.
Co-reporter:Ran Ban, Yanli Liang, Pengtao Ma, Dongdi Zhang, Jingyang Niu, Jingping Wang
Inorganic Chemistry Communications 2016 Volume 71() pp:65-67
Publication Date(Web):September 2016
DOI:10.1016/j.inoche.2016.07.003
•HEDP-based polyoxovanadate•Ring-shaped structure, 1-D double-chains, 2-D wavy-plane•Magnetic propertyA novel organophosphonate-based polyoxovanadate, Cs1·5Na3.5[H{V3(H2O)O3}{O3PC- (OH)(CH3)PO3}3]·15H2O (1) has been synthesized and further investigated by single-crystal X-ray diffraction analysis, IR spectrum, UV–vis spectroscopy, X-ray powder diffraction, thermogravimetric analysis and X-ray photoelectron spectroscopy. Single-crystal X-ray analysis reveals that compound 1 crystallizes in the triclinic space group P-1 with a = 9.506(3) Å, b = 15.150(5) Å, c = 17.915(6) Å, V = 2437.9(14) Å3 and Z = 2. Compound 1 exhibits a ring-shaped cluster with three branches of the 1-hydroxyethane 1, 1-diphosphonic acid [HEDP = H2O3P(OH)C(CH3)PO3H2] ligands. Furthermore, the magnetic property of compound 1 has also been studied.Polyanion 1a consists of three HEDP fragments and three {V(H2O)n} bridges, which are connected alternatively into a ring-shaped structure. Interestingly, an isosceles triangle is constructed by V1, V2 and V3 atoms.
Co-reporter:Rong Wan, Yueyan Wang, Mengdan Han, Pengtao Ma, Jingyang Niu, Jingping Wang
Inorganic Chemistry Communications 2016 Volume 68() pp:72-75
Publication Date(Web):June 2016
DOI:10.1016/j.inoche.2016.04.011
•Nickel-substituted polyoxotungstate•Cubane-type structure•Magnetic propertyA novel cubane-type Ni-substituted polyoxotungstate based on trivacant Dawson-type [P2W15O56]12 − unit with the formula of Na4H4[P2W15O56(W0.5Ni3.5)(OH)6(H2O)3]·18.5H2O (1) has been synthesized in aqueous medium and characterized by IR spectroscopy, EDX spectrum, thermogravimetric analysis and magnetic measurements. Structural analysis indicates that 1 consists of a trivacant Dawson-type unit [P2W15O56]12 − incorporated in a cubane-type {Ni3.5W0.5O7(OH)6(H2O)3} group. Magnetic studies show that the ferromagnetic NiNi exchange interactions exist in the cubane-type cluster.A novel cubane-type Ni-substituted polyoxotungstate based on trivacant Dawson-type unit has been synthesized, which consists of a trivacant Dawson-type [P2W15O56]12 − incorporated in a cubane-type {Ni3.5W0.5O7(OH)6(H2O)3} cluster.
Co-reporter:Yanfen Liang, Suzhi Li, Donghui Yang, Pengtao Ma, Jingyang Niu and Jingping Wang
Journal of Materials Chemistry A 2015 vol. 3(Issue 18) pp:4632-4639
Publication Date(Web):26 Mar 2015
DOI:10.1039/C5TC00297D
A series of inorganic–organic hybrid heteropolyoxomolybdates built from [TeMo6O21]2− polyoxoanions and multicarboxylic acids including (C3N2H5)4H6[(TeMo6O21)2{O2C(CH2)2CO2}3]·9.5H2O (1), (C3N2H5)8H2[(TeMo6O21)2{O2C(CH2)6CO2}3]·3.5H2O (2) and (CN3H4)16H4[(TeMo6O21)4{C6H3(COO)3}4]·16H2O (3) have been synthesized arising from the reactions of (NH4)6Mo7O24·4H2O, Na2TeO3/TeO2 and the corresponding multicarboxylic acids in an aqueous medium. X-ray single crystal diffraction, X-ray powder diffraction (XPRD), elemental analyses, inductively coupled plasma (ICP) spectra, IR spectra, UV spectra and thermogravimetric (TG) analyses have been implemented. Crystal structure analyses reveal that both compounds 1 and 2 are dimers, while 3 is a tetramer, however, they contain the same {TeMo6} unit which consists of a six-membered MoO6 octahedral ring capped by one {TeO3} trigonal pyramid. Compounds 1–3 exhibit intriguing allochroic properties. They can change color from white to blue/green when heated. Upon the irradiation of a xenon lamp (full wave-band, P = 300 W), their color can change from white to reddish brown.
Co-reporter:Yu Huo, Zhiyuan Huo, Pengtao Ma, Jingping Wang, and Jingyang Niu
Inorganic Chemistry 2015 Volume 54(Issue 2) pp:406-408
Publication Date(Web):December 29, 2014
DOI:10.1021/ic502404m
A S-shaped organotriphosphonate polyoxotungstate, K4H6[H4{(AsW9O33)Zn(H2O)W5O11(N(CH2PO3)3)}2(μ2-O)2]·27H2O (1), has been synthesized and characterized. Compound 1 contains a different geometry of [{Zn(H2O)W5O19(N(CH2PO3)3)}]12– clusters, which forms a chiral conformation. The catalysis of 1 for alkene epoxidation was investigated with a hydrogen peroxide (H2O2) oxidant.
Co-reporter:Yuan Wang, Xiaopeng Sun, Suzhi Li, Pengtao Ma, Jingyang Niu, and Jingping Wang
Crystal Growth & Design 2015 Volume 15(Issue 5) pp:2057-2063
Publication Date(Web):March 26, 2015
DOI:10.1021/cg5012499
Eight members of a new family of polyoxometalate (POM)-ligated organic–inorganic rare earth metal compounds K11LiH21[RE3(H2O)7{RE2(H2O)4As2W19O68(WO2)2(C6O7H4)2}3]·nH2O (RE = Y (1), Tb (2), Dy (3), Ho (4), Er (5), Tm (6), Yb (7), Lu (8); for compounds 1–6 and 8, n = 46; for compound 7, n = 57; C6H8O7 = citric acid) have been synthesized through conventional aqueous solution by introducing organic ligand citric acid into the arsenotungstates system, which were further characterized by elemental analyses, IR and UV spectroscopy, thermogravimetric analyses, and single-crystal X-ray diffraction. The polyoxoanions [RE3(H2O)7{RE2(H2O)4As2W19O68(WO2)2(C6O7H4)2}3]33– in compounds 1–8 are composed of three {RE2(H2O)4As2W19O68{WO2(C6O7H4)}2} subunits linked by another three rare earth ions. What’s more, the fluorescence properties of 2 and 3 have also been investigated. Electron paramagnetic resonance (EPR) experiments further demonstrated the result of the interesting photochromic property.
Co-reporter:Pengtao Ma, Rong Wan, Yanan Si, Feng Hu, Yueyan Wang, Jingyang Niu and Jingping Wang
Dalton Transactions 2015 vol. 44(Issue 25) pp:11514-11523
Publication Date(Web):13 May 2015
DOI:10.1039/C5DT01323B
Five members of a new family of polyoxometalate (POM)-ligated trinuclear lanthanoid (Ln) clusters with the general formula K20Li2[Ln3(μ3-OH)(H2O)8(AsW9O33)(AsW10O35(mal))]2·17H2O [Ln = Dy (1Dy), Tb (2Tb), Gd (3Gd), Eu (4Eu), and Sm (5Sm), mal = malate] have been synthesized, all of which consist of the dimeric {[Ln3(μ3-OH)(H2O)8(AsW9O33)[AsW10O35(mal)]}11− polyanion constructed from a {AsW9O33} and a {AsW10O35(mal)} building block linked by a tri-Ln cluster [Ln3(μ3-OH)(H2O)8]8+, where the two malate ligands play a key bridging role. The {AsW10O35(mal)} subunit can be viewed as the {AsW9O33} building block anchoring an additional tungsten center [WO2(mal)]. The electrospray ionization mass (ESI-MS) spectra indicate that the dimeric fragments of 1Dy and 2Tb are unstable, which are apt to produce the subunit [KH5Ln3(OH)(H2O)(AsW9O33)2]4− in solution. The solid-state photoluminescence measurements display the yellowish green emission for 1Dy and 5Sm, green emission for 2Tb and reddish orange emission for 4Eu, which are attributed to the LnIII f–f electron transitions. Magnetic property studies indicate that 1Dy displays probable SMM behaviour with slow magnetization relaxation, whereas the weak antiferromagnetic interactions exist in two {Ln3} clusters for 2Tb–5Sm.
Co-reporter:Shumin Chen, Ying Liu, Jipeng Guo, Pengzhen Li, Zhiyuan Huo, Pengtao Ma, Jingyang Niu and Jingping Wang
Dalton Transactions 2015 vol. 44(Issue 22) pp:10152-10155
Publication Date(Web):07 May 2015
DOI:10.1039/C5DT01046B
A multi-component polyoxometalate based on earth-abundant elements (NH4)10[Co8(H2O)10V10Mo23O104(OH)6]·34.5H2O (1) has been successfully obtained and characterized. Furthermore, compound 1 acted as a Lewis acid catalyst and promoted the conversion of carbon dioxide to a cyclic carbonate under mild reaction conditions.
Co-reporter:Yuan Wang, Pengtao Ma and Jingyang Niu
Dalton Transactions 2015 vol. 44(Issue 10) pp:4679-4682
Publication Date(Web):30 Jan 2015
DOI:10.1039/C4DT02967D
A series of organic–inorganic hybrid rare earth complexes {[RE2(PO)2(H2O)10][H2Mo36O112(OH2)12(PO)4]}·5PO·2(CH3CN)·nH2O [n = 23–42, RE(III) = Nd(III), 1; Sm(III), 2; Eu(III), 3; Gd(III), 4; Dy(III), 5; Er(III), 6; Tm(III), 7; Yb(III), 8; Lu(III), 9; Y(III), 10; PO = piperidin-2-one] have been synthesized and fully characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, IR spectra, thermogravimetric analysis and UV-vis spectra. Structural analysis reveals that compounds 1–10 are isostructural and crystallize in the monoclinic P2(1)/n space group. Each compound contains a centrosymmetric anionic cluster [Mo36O112(OH2)12(PO)4]8−, which could be described as the derivative of [Mo36O112(OH2)16]8− with four water molecules substituted by organic PO molecules. Each {Mo18} subunit connects with one RE(III) ion via its two terminal O atoms from two independent {MoO6} octahedra. The eight coordinated RE(III) ion with a distorted tetragonal antiprism coordination geometry is also surrounded by another six oxygen atoms, five of them from five water molecules and the final one from one PO molecule. Compounds 1–10 show considerable photosensitive behavior under visible light excitation. In addition, compound 3 exhibits three emission bands at 580, 595 and 617 nm in the solid state, which could be assigned to 5D0→7F0, 5D0→7F1 and 5D0→7F2 transitions of Eu(III) ions, respectively.
Co-reporter:Yuan Wang, Xiaopeng Sun, Suzhi Li, Pengtao Ma, Jingping Wang and Jingyang Niu
Dalton Transactions 2015 vol. 44(Issue 2) pp:733-738
Publication Date(Web):04 Nov 2014
DOI:10.1039/C4DT01703J
Six tartrate-bridging rare-earth-substituted polytungstoarsenates [RE2(C4H4O6)(C4H2O6)(As W9O33)]218− (HoIII (1), ErIII (2), TmIII (3), YbIII (4), LuIII (5), and YIII (6)) have been synthesized under conventional solution conditions. They have been further characterized by elemental analyses, X-ray powder diffraction (XRPD), IR and UV-vis spectroscopy and single-crystal X-ray diffraction. Preliminary variable-temperature magnetic susceptibility measurements indicate that 1–4 exhibit antiferromagnetic coupling.
Co-reporter:Ling Yang, Qisen Liu, Pengtao Ma, Jingyang Niu and Jingping Wang
Dalton Transactions 2015 vol. 44(Issue 30) pp:13469-13472
Publication Date(Web):26 Jun 2015
DOI:10.1039/C5DT00262A
An unprecedented silicotungstate trimer K9[H14{SiW10MnIIMnIIIO38}3(CO3)]·39H2O (1) has been successfully synthesized, in which the CO32− resides inside the three Keggin {SiW10MnIIMnIIIO38} units and the three O atoms serve as μ2-O atoms to connect with three MnIII. Magnetic investigation indicates that 1 exhibits antiferromagnetic coupling.
Co-reporter:Xiaopeng Sun, Zhijie Liang, Pengtao Ma, Ran Ban, Mingshuang Jiang, Dongdi Zhang, Jingping Wang and Jingyang Niu
Dalton Transactions 2015 vol. 44(Issue 40) pp:17544-17550
Publication Date(Web):08 Sep 2015
DOI:10.1039/C5DT02471D
A novel organophosphonate-functionalized heteropolyoxomolybdate incorporated nickel cluster, CsNa9[H2{Ni3O2(H2O)6}(PMo6O21)2{Ni(OOCCH2NHCH2PO3)2}3]·21H2O (1), has been synthesized, which represents the first member of the family of oxomolybdenum organophosphonate containing hexa-nuclear Ni(II) in a polyanion framework. The polyanion comprises a unique ladder-type {Ni3O10(H2O)6} cluster and three {Ni(OOCCH2NHCH2PO3)2} bridgings, which are capped on either end by a {PMo6O28} group. Photocatalytic experiments indicate that 1 exhibits catalytic activity for the photodegradation of RhB solution. Furthermore, magnetic studies indicate that 1 displays antiferromagnetic interactions.
Co-reporter:Zhiyuan Huo, Jipeng Guo, Jingkun Lu, Qiaofei Xu, Pengtao Ma, Juan Zhao, Dongdi Zhang, Jingyang Niu and Jingping Wang
RSC Advances 2015 vol. 5(Issue 84) pp:69006-69009
Publication Date(Web):31 Jul 2015
DOI:10.1039/C5RA14201F
A nona-vacant Keggin-type tricarbonyl rhenium derivative [(NH4)5]{[PMo3O16][Re(CO)3]4}·1.5H2O was obtained and characterized. Its frontier orbitals were computed by density functional theory (DFT) calculations. Furthermore, it could act as a Lewis acid catalyst and promote the conversion of CO2 to cyclic carbonate under mild reaction conditions with pyrrolidinium bromide as a co-catalyst.
Co-reporter:Xiaopeng Sun, Donghui Yang, Gaigai Wang, Zhijie Liang, Pengtao Ma, Jingping Wang and Jingyang Niu
RSC Advances 2015 vol. 5(Issue 40) pp:31392-31398
Publication Date(Web):19 Mar 2015
DOI:10.1039/C5RA01955A
The nature of carboxylic acid has a profound effect on constructing POM-based architectures. With different carboxylic acid ligands, three novel diphosphonate-containing compounds have been synthesized and further investigated by elemental analyses, single-crystal X-ray diffraction, IR spectroscopy, UV-vis spectroscopy, X-ray powder diffraction (XRPD), 31P NMR spectroscopy, cyclic voltammetric behavior and thermogravimetric (TG) analyses. [(HO3PCH2PO3)Mo6O18(O2CC6H4OH)2]5− (1a) shows a ring-shaped cluster with a {Mo6} plane framework. [{(HO3PCH2PO3)Mo6O18(CH3CO2)2}2Na2(H2O)2]8− (2a) is a reverse symmetrical “crown-type” structure and the subunits are linked by two Na–O(1W)–Na bridges. The polyanion [{(O3PCH2PO3)(Mo6O18(H2O)2)(O2CCH2CO2)}2(Mo2O5)2(μ3-O)2]12− (3a) appears as an “S-shaped” structure with a centre of inversion.
Co-reporter:Yu Huo, Dandan Li, Rong Wan, Pengtao Ma, Dongdi Zhang, Jingyang Niu and Jingping Wang
RSC Advances 2015 vol. 5(Issue 128) pp:106077-106082
Publication Date(Web):01 Dec 2015
DOI:10.1039/C5RA20806H
A new family of organotriphosphonate-functionalized TM-containing polyoxotungstates, K4H6[H4{(AsW9O33)TM(H2O)W5O11(N(CH2PO3)3)}2(μ2-O)2]·24H2O [TM = Ni (1), Co (2), Mn (3)], have been synthesized from the preformed POM precursor [As2W19O67(H2O)]14−. They were thoroughly characterized by single crystal X-ray diffraction, IR and UV spectra, thermogravimetric (TG), X-ray powder diffraction (XRPD), X-ray photoelectron spectroscopy (XPS) and elemental analyses. The structures are comprised of two Wells–Dawson building blocks in opposite directions that are connected by two μ2-oxo groups acting as a “hinge”, with the two ATMP ligands serving as a stanchion. The electrochemical behavior of these compounds has also been investigated.
Co-reporter:Zhijie Liang, Dongdi Zhang, Qisen Liu, Pengtao Ma, Jingyang Niu, Jingping Wang
Inorganic Chemistry Communications 2015 Volume 54() pp:19-20
Publication Date(Web):April 2015
DOI:10.1016/j.inoche.2015.01.033
•The first two-nuclear sandwiched PONb•The combination of hydrothermal technique and diffusion method•The photocatalytic property was studied.•The bridging oxygen atom Ob is the most reactive of [Nb6O19]8 −.A novel transition-metal (TM) complex based on Lindqvist polyoxoniobate K10[(Nb6O19)CrIII(H2O)2]2·28H2O (1) has been synthesized by a new two-pot synthesis strategy and structurally characterized by single crystal X-ray diffraction analysis, IR spectrum, UV–vis spectroscopy, XRPD and TG analysis. Compound 1 crystallizes in the C2/m space group with a = 32.143(19) Å, b = 10.030(6) Å, c = 12.878(8) Å, β = 110.611(9)°, and V = 3886(4) Å3. X-ray structure analysis reveals that polyanion [(Nb6O19)CrIII(H2O)2]210 − (1a) represents the first example of two nuclear dimeric polyoxoniobate, in which two Lindqvist anions [Nb6O19]8 are sandwiched by two {CrIII(H2O)2} groups. Further, 1 exhibits photocatalytic H2 evolution activity.The first two-nuclear sandwich PONb, K10[(Nb6O19)CrIII(H2O)2]2·28H2O (1), has been synthesized, and the photocatalytic activity of 1 has also been studied.
Co-reporter:Pengtao Ma, Yanan Si, Rong Wan, Shaowei Zhang, Jingping Wang, Jingyang Niu
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2015 Volume 138() pp:579-584
Publication Date(Web):5 March 2015
DOI:10.1016/j.saa.2014.12.001
•The 1-D linear chainlike framework.•Lanthanide-substituted polyoxometalate.•Terbium photoluminescent property.•ESI-MS spectrum in solution.A new 1-D linear chainlike terbium-substituted polyoxometalate [Tb(H2O)2(α-PW11O39)]4− (1) has been synthesized in aqueous solution and characterized by elemental analysis, inductively coupled plasma atomic emission spectrometry (ICP-AES), X-ray powder diffraction (XRPD), IR spectrum, thermal analysis, electrospray ionization mass spectrometry (ESI-MS), and X-ray single-crystal diffraction. X-ray structural analysis reveals that 1 displays a 1-D linear chain containing [Tb(H2O)2(α-PW11O39)]4− moieties. The Tb(III) cation incorporated into the monolacunary Keggin-type [α-PW11O39]7− unit resides in a distorted monocapped triangular prismatic geometry and acts as a linker to join two adjacent [α-PW11O39]7− units to form a 1-D chain structure. Solid-state photoluminescent property of 1 has been investigated at room temperature and the photoluminescent emission mainly results from the synergistic effect of the TbIII cation and the Na7[α-PW11O39] precursor. The ESI-MS spectrum of 1 confirms that the polyanion [Tb(H2O)(HPW11O39)]3− is stable in aqueous solution.
Co-reporter:Qiuxia Han, Xueping Sun, Jie Li, Pengtao Ma, and Jingyang Niu
Inorganic Chemistry 2014 Volume 53(Issue 12) pp:6107-6112
Publication Date(Web):June 6, 2014
DOI:10.1021/ic5004879
A novel polyoxometalate-based metal organic framework (POMOF) constructed from isolated isopolyoxotungstate [H2W11O38]8– cluster, {[Cu2(bpy)(H2O)5.5]2[H2W11O38]·3H2O·0.5CH3CN} (1, where bpy = 4,4′-bpydine), has been synthesized under solvothermal conditions and charaterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction. In 1, {W11} clusters are alternately linked by two [Cu(2)(H2O)1.5(Ot)3(N)]2+ cations in an unexpected end-to-end fashion leading to a one-dimensional (1D) chain. Adjacent 1D chains are linked through Cu(1)–bpy–Cu(2) in an opposite direction to form a two-dimensional (2D) wavelike sheet along the ab plane. These 2D sheets are further stacked in a parallel fashion giving rise to the 1D channels with copper(II) cations aligned in the channels. The resulting POMOF acted as a Lewis acid catalyst through a heterogeneous manner to prompt cyanosilylation with excellent efficiency.
Co-reporter:Dongdi Zhang, Zhijie Liang, Songqiang Xie, Pengtao Ma, Chao Zhang, Jingping Wang, and Jingyang Niu
Inorganic Chemistry 2014 Volume 53(Issue 18) pp:9917-9922
Publication Date(Web):August 29, 2014
DOI:10.1021/ic501575x
A structurally intriguing polyanion, [{Nb4O6(OH)4}{Nb6P2W12O61}4]36– (2), was directly formed by controlling the reaction parameters and characterized by single-crystal X-ray diffraction, IR spectroscopy, and elemental analyses. Polyanion 2 is the first niobium-substituted Wells–Dawson-based tetramer and contains the largest Nb28 cluster encapsulated by four hexalacunary Wells–Dawson frameworks. The activities of compounds Na12[H24-2]·24H2O (2a), K12[H2P2W12O48]·24H2O, and K7[HNb6O19]·13H2O against three human tumor cell lines were investigated in vitro. The preliminary results revealed that 2a could efficiently inhibit the growth of the human breast cancer MCF-7 cells. Interestingly, the activity of 2a is significantly better than those of the simple reagents.
Co-reporter:Qiuxia Han, Xueping Sun, Jie Li, Pengtao Ma, and Jingyang Niu
Inorganic Chemistry 2014 Volume 53(Issue 4) pp:2006-2011
Publication Date(Web):January 30, 2014
DOI:10.1021/ic402179u
By reaction of [As2W19O67(H2O)]14–, NiCl2·6H2O, and phen under hydrothermal conditions, a new organic–inorganic tungstoarsenate hybrid [Ni(phen)3]4[As2W18O60]{[Ni(phen)2][H2As2W18O60]}·12H2O (where phen = 1,10-phenanthroline) (1) was obtained via self-assembly and characterized by elemental analysis, infrared (IR) spectroscopy, solid UV–vis absorption spectrum, and single-crystal X-ray diffraction (XRD). An unprecedented 18-tungstoarsenate Dawson cluster, β-[W18O54(AsO3)2]6–, encapsulating two pyramidal arsenite AsO33– anions as templates and exhibiting interesting intramolecular As···As interaction is first achieved. 1 displays a one-dimensional (1D) chain architecture constructed by alternating β-[W18O54(AsO3)2]6– and nickel(II) complexes [Ni(phen)2)]2+. The resulting hybrid can act as a photocatalyst to prompt the degradation of Rhodamine B (RhB) with excellent efficiency.
Co-reporter:Donghui Yang, Yanfen Liang, Pengtao Ma, Suzhi Li, Jingping Wang, and Jingyang Niu
Inorganic Chemistry 2014 Volume 53(Issue 6) pp:3048-3053
Publication Date(Web):February 21, 2014
DOI:10.1021/ic402882a
Four new inorganic–organic hybrids, namely, (NH4)3H3[AsMo6O21(O2CC6H4NH2)3]·8.5H2O (1), (NH4)16H3[(AsMo6O21)3(O2CCH2CO2)5]·18H2O (2), (NH4)11H[(AsMo6O21)2{O2C(CH2)6CO2}3]·8H2O (3), and (NH4)18H6[(AsMo6O21)4{C6H3(CO2)3}4]·24.5H2O (4), were synthesized by reaction of As2O3 with (NH4)6Mo7O24·4H2O and organic components in aqueous medium. All of the four hybrids feature a common {AsMo6} unit composed of a six-membered MoO6 octahedral ring capped by one {AsO3} trigonal pyramid. Although these hybrids exhibit similar chemical formula, their structures are monomer, dimer (capsule), trimer, and tetramer (cage), respectively, depending upon the nature of carboxylic acids. Also, the assembly processes appear to be highly versatile and sensitive to the inherent nature of carboxylic acids, which direct the assemblies toward construction of POM clusters and participate directly to their stabilization. In addition, successful isolation of these hydrids shows that it would be possible to achieve a variety of structural predesign in this inorganic–organic system by means of a ligand design route based on the interplay between the organic molecules and polyoxometalates (POMs).
Co-reporter:Qiaohua Geng, Qisen Liu, Pengtao Ma, Jingping Wang and Jingyang Niu
Dalton Transactions 2014 vol. 43(Issue 26) pp:9843-9846
Publication Date(Web):29 Apr 2014
DOI:10.1039/C4DT00875H
An unprecedented arsenic-disubstituted Lindqvist-type peroxopolyoxoniobate Cs2.5Na2{As2Nb4(O2)4O14H1.5}·11H2O has been successfully synthesized and characterized. The photocatalytic activity of the cluster for H2 evolution from water is investigated by irradiating with a 300 W Xe lamp, which shows a certain photocatalytic water splitting activity.
Co-reporter:Nan Zhang, Yanxue Tai, Mingxue Li, Pengtao Ma, Junwei Zhao and Jingyang Niu
Dalton Transactions 2014 vol. 43(Issue 13) pp:5182-5189
Publication Date(Web):10 Jan 2014
DOI:10.1039/C4DT00077C
Up to now, the metal complexes with thiocarbonohydrazones have been comparatively rare. Herein, three main group monometallic complexes formulated as [Bi(HL)(NO3)2(H2O)] (1), [Ga(HL)2]OAc·EtOH (2) and [(Ph)2Sn(HL)(OAc)]·DMF (3), where H2L = bis(2-acetylpyrazine)thiocarbonohydrazone, have been synthesized and characterized. The crystal structures of complexes 2 and 3 have been determined by single-crystal X-ray diffraction. Growth inhibition assays have indicated that both the free ligand and the title complexes are capable of inhibiting cell proliferation growth and could slightly distinguish the human hepatocellular carcinoma HepG2 cells from normal hepatocyte QSG7701 cells. Of particular note is the fact that the bismuth(III) complex 1 is the most active compound of this study and is 14-fold more cytotoxic than H2L with an IC50 value of 2.96 ± 0.25 μM. Its possible apoptotic mechanism has been evaluated in HepG2 cells. Complex 1 promotes a dose-dependent apoptosis in HepG2 cells and the apoptosis is associated with an increase in intracellular reactive oxygen species (ROS) production and reduction of mitochondrial membrane potential (MMP).
Co-reporter:Donghui Yang, Yanfen Liang, Pengtao Ma, Suzhi Li, Jingping Wang and Jingyang Niu
CrystEngComm 2014 vol. 16(Issue 34) pp:8041-8046
Publication Date(Web):16 Jun 2014
DOI:10.1039/C4CE00580E
We report a simple and efficient approach to incorporate organic groups into polymolybdates by reaction of H3PO3 with Na2MoO4·2H2O/(NH4)6Mo7O24·4H2O and organic components in aqueous medium. Carboxylate and alcoholate ligands were covalently attached to the [HPMo6O21]2− cluster to generate a series of inorganic–organic hybrid phosphomolybdates. Depending on the successful synthesis of these structures, it could be possible to obtain a variety of these hybrids through rational structural design using ligand control, which is rare in traditional “one-pot” polyoxometalate (POM) synthesis.
Co-reporter:Suzhi Li, Yuan Wang, Pengtao Ma, Jingping Wang and Jingyang Niu
CrystEngComm 2014 vol. 16(Issue 47) pp:10746-10749
Publication Date(Web):16 Oct 2014
DOI:10.1039/C4CE01577K
The large, lanthanide-containing polyoxometalate–carboxylate hybrid K14Li4H20[As6W58O206Ce4(pydc)2(H2O)6]·44H2O (1) (H2pydc = pyridine-2,3-dicarboxylic acid) was synthesized from the versatile precursor [As2W19O67(H2O)]14− through combined disassembly and reassembly processes. The novel macroanion in 1 constitutes two identical subunits with the formula [As3W29O103Ce2(pydc)(H2O)3]19−.
Co-reporter:Ruimin Xing, Fenglan Xu, Shanhu Liu, Jingyang Niu
Materials Letters 2014 Volume 134() pp:71-74
Publication Date(Web):1 November 2014
DOI:10.1016/j.matlet.2014.07.035
•Glossy, cluster and hollow nanospheres were synthesized in a similar solvothermal procedure.•The morphology could be regulated by the addition of different alkali sources without any additional additives/surfactants involved.•A plausible mechanism based on chelation and local Ostwald ripening is proposed.Three different magnetite nanospheres including glossy nanospheres, cluster nanospheres and hollow nanospheres were prepared in the similar solvothermal procedure. Such a process is very simple and controllable without any template or surfactants involved; only the necessary alkali source for the magnetite synthesis was employed as shape-controlled reagent. X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), N2 adsorption–desorption analysis and a superconducting quantum interference device magnetometer (SQUID) were used to characterize the composition, morphologies, and properties of these nanospheres. Furthermore, the effects of different types of basic reagents on the morphologies were discussed; the pH value and local Ostwald ripening were presumed to be key factors to determine the three different shapes of Fe3O4 nanospheres.
Co-reporter:Yu Huo, Lu Yang, Jingyang Niu, Jingping Wang
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2014 Volume 131() pp:484-489
Publication Date(Web):15 October 2014
DOI:10.1016/j.saa.2014.04.063
•1 Represents the first case of transition-metal–organic ligands polyoxomolybdates.•There exist weak π–π interactions among the bipyridine groups.•Three CuII ions in 1 display five- and six-coordinate environments.•Luminescent property shows the presence of LMCT transitions.An organic–inorganic hybrid polyoxomolybdate with formula as [Cu(2,2′-bpy)(H2O)]2[Cu(2,2′-bpy)(H2O)3][(O3PCCH3(OH)PO3)2MoVI4O11(H2O)2]·7H2O (1) (2,2′-bpy = 2,2′-bipyridine) has been successfully synthesized constructing by diphosphonate H2O3PC(CH3)(OH)PO3H2 (1-hydroxyethylidene-1,1-bisphosphonic acid, noted as HEDP or etidronate) under conventional aqueous solution. 1 was characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, thermogravimetric (TG) analysis, and X-ray photoelectron spectroscopy (XPS). Each anion cluster of 1 can be regarded as the fusion of two [{Cu(2,2′-bpy)(H2O)}(O3PCCH3(OH)PO3)MoVI2O6]2− subunits with an additional six-coordinated [Cu(2,2′-bpy)]2+ coordination cation linking on one side and there exist weak π–π interactions among the bipyridine groups. The XPS spectra indicate that the oxidation states of Mo and Cu in 1 are +6 and +2, respectively. Photoluminescence properties of 1 and the free 2,2′-bipyridine ligand have been both analyzed, showing that the presence of ligand-to-metal-charge-transfer (LMCT) transitions and metal–ligand coordination have an important effecting on the photoluminescence.
Co-reporter:Zhiyuan Huo;Juan Zhao; Zhanwei Bu;Pengtao Ma;Qisen Liu; Jingyang Niu; Jingping Wang
ChemCatChem 2014 Volume 6( Issue 11) pp:3096-3100
Publication Date(Web):
DOI:10.1002/cctc.201402575
Abstract
A monovacant Keggin-type polyoxometalate-supported trirhenium carbonyl derivate [(CH3)4N]5H23[(PW11O39){Re(CO)3}3(μ3-O)(μ2-OH)]4⋅24 H2O was synthesized. It was used as a catalyst for the synthesis of cyclic carbonates from carbon dioxide and epoxides under mild reaction conditions with co-catalyst pyrrolidinium bromide. The catalyst system was recycled 10 times with only a small decline in yield. The catalytic mechanism was hypothesized based on experimental results and the frontier orbitals computed by DFT calculations.
Co-reporter:Zhen Zhou, Dongdi Zhang, Lu Yang, Pengtao Ma, Yanan Si, Ulrich Kortz, Jingyang Niu and Jingping Wang
Chemical Communications 2013 vol. 49(Issue 45) pp:5189-5191
Publication Date(Web):18 Apr 2013
DOI:10.1039/C3CC41628C
The nona-CuII-containing tungstoarsenate(III) [H4{CuII9AsIII6O15(H2O)6}(α-AsIIIW9O33)2]8− (1a) has been synthesized and characterized. Polyanion 1a comprises a unique, cylindrical {CuII9AsIII6O15(H2O)6}6+ cluster, which forms a large central cavity and is capped on either end by an [α-AsIIIW9O33]9− capping group. It exhibits remarkable activity against K562 leukaemia cells, as well as induces HepG2 cell apoptosis and autophagy.
Co-reporter:Lu Yang, Pengtao Ma, Zhen Zhou, Jingping Wang, and Jingyang Niu
Inorganic Chemistry 2013 Volume 52(Issue 15) pp:8285-8287
Publication Date(Web):July 17, 2013
DOI:10.1021/ic400848r
A crown-shaped organic–inorganic hybrid polyoxomolybdate, Na5[H7{N(CH2PO3)3}Mo6O16(OH) (H2O)4]4·18H2O (1) has been presented and characterized. Such an intriguing structure consists of a 24-molybdenum-membered polyanion constructed by organotriphosphonate ligands, which represents the highest nuclearity of metal atoms in the area of organophosphonate-based polyoxometalates.
Co-reporter:Donghui Yang ; Suzhi Li ; Pengtao Ma ; Jingping Wang ;Jingyang Niu
Inorganic Chemistry 2013 Volume 52(Issue 24) pp:14034-14039
Publication Date(Web):December 3, 2013
DOI:10.1021/ic401804e
The chemical system based on [SeMo6O21]4– polyanion and carboxylate ligand has been investigated. According to the inherent nature of organic groups, a series of selenomolybdates with three architectures have been isolated through rational and deliberate synthetic routes by stereospecific addition of different carboxylic acids. Such an approach is potentially interesting for {SeMo6} cluster, which exhibits a high surface nucleophilicity and is capable of being functionalized by covalently bound carboxylic acids. Investigation of the assemblies reveals that carboxylic acids have good flexibility and conformational freedom, representing the powerful chemical tools to control the polyanion assembly processes.
Co-reporter:Donghui Yang, Suzhi Li, Pengtao Ma, Jingping Wang, and Jingyang Niu
Inorganic Chemistry 2013 Volume 52(Issue 15) pp:8987-8992
Publication Date(Web):July 11, 2013
DOI:10.1021/ic401176j
The [HPMo6O21]2– units and carboxylate linkers can be combined to build novel polyanions by a carefully designed complementary system in self-assembly processes depending only on the number of carboxyl groups and the nature of carboxylic acids. Complexes (NH4)5[HPMo6O21(O2CC6H4OH)3]·4H2O (1), (NH4)8H2[(HPMo6O21)2(C2O4)3]·13H2O (2), (NH4)20[(HPMo6O21)4(O2CCH2CO2)6]·17H2O (3), and Cs2(NH4)10[(HPMo6O21)2(HPO3){C6H3(CO2)3}2]·5H2O (4) have been synthesized by a simple one-pot reaction of (NH4)6Mo7O24·4H2O, H3PO3, and carboxylic acid ligands in aqueous solution. Formation of these compounds is critically dependent on the identifying carboxylic acids, which play the important templated role in assembly processes. The stability of these clusters was explored using electrospray ionization mass spectrometry (ESI-MS) and 31P NMR spectroscopy, and electron paramagnetic resonance (EPR) experiments further demonstrated the result of the interesting photochromic property.
Co-reporter:Dongdi Zhang, Juan Zhao, Yanhui Zhang, Xiaojing Hu, Longsheng Li, Pengtao Ma, Jingping Wang and Jingyang Niu
Dalton Transactions 2013 vol. 42(Issue 8) pp:2696-2699
Publication Date(Web):07 Jan 2013
DOI:10.1039/C2DT32678G
Two novel octamolybdate-based tricarbonyl metal derivatives have been successfully synthesized and characterized, which represent the first two examples of tricarbonyl metal groups attached to a new {Mo8O30} building block.
Co-reporter:Xiang Ma, Pengtao Ma, Dongdi Zhang, Jiai Hua, Chao Zhang, Tengfei Huang, Jingping Wang and Jingyang Niu
Dalton Transactions 2013 vol. 42(Issue 4) pp:874-878
Publication Date(Web):12 Nov 2012
DOI:10.1039/C2DT32061D
A cage-like {[Ca(H2O)]6(H2O)}12+ cluster with a water molecule enwrapped, sandwiched by two novel [As4W6O34]12− fragments, has been obtained, and the extension of these clusters from molecules into a 2-D layer occurs through [Ca(H2O)5]2+ linkers, which represents the first heteropolyoxoanion (HPA) constituted by [As4W6O34]12− and the unprecedented high nuclearity {[Ca(H2O)]6(H2O)}12+ cluster.
Co-reporter:Lu Yang, Zhen Zhou, Pengtao Ma, Jingping Wang and Jingyang Niu
CrystEngComm 2013 vol. 15(Issue 27) pp:5452-5457
Publication Date(Web):09 May 2013
DOI:10.1039/C3CE40228B
Two hexanuclear molybdophosphonates, Na2H4{(CH3COO)[N(CH2PO3)3]Mo6O17(OH)}·13H2O (1) and Na2(NH4)4[Mn2Na2(H2O)2]{[HN(CH2PO3)2](CH3COO)PMo6O22}2·16H2O (2), have been successfully synthesized and characterized by X-ray crystallography, elemental analysis, IR spectra and XRPD, along with a 31P NMR spectroscopic study for 1 and a magnetic susceptibility study for 2. Compounds 1 and 2 are prepared in solution by the self-assembly of the amino trimethylene phosphonic acid (noted as ATMP) ligand and heptamolybdate. Compound 1 exhibits a ring-shaped cluster with two branches of the ligand bound off-center, while the introduction of Mn ions breaks the central P–C bond to form a dinuclear Mn(II) sandwich-type polyanion 2. The magnetic susceptibility of 2 shows strong antiferromagnetic interactions between the two MnII cores.
Co-reporter:Lanying Song, Dongdi Zhang, Pengtao Ma, Zhijie Liang, Jingping Wang and Jingyang Niu
CrystEngComm 2013 vol. 15(Issue 23) pp:4597-4600
Publication Date(Web):08 Apr 2013
DOI:10.1039/C3CE40343B
Two lanthanide-containing peroxoisopolyanions [Ln4(WO4)(H2O)16{W7O22(O2)2}4]14− (Ln = LaIII; PrIII), have been synthesized by reaction of Na2WO4 and lanthanide (Ln) ions in the presence of peroxide. These represent the first two examples of peroxo-containing Ln-stabilized polyanions (LSPs), and have the highest number of W atoms among all known Ln-stabilized isopolytungstates (IPTs) as well.
Co-reporter:Shaowei Zhang, Dongdi Zhang, Pengtao Ma, Yanfen Liang, Jingping Wang and Jingyang Niu
CrystEngComm 2013 vol. 15(Issue 15) pp:2992-2998
Publication Date(Web):13 Feb 2013
DOI:10.1039/C3CE27024F
Three unprecedented trimers based on monovacant Dawson-type polyoxotungstates Na12[Ln(H2O)9]2[(α2-P2W17O61H4)La(H2O)4]6·100H2O (Ln = LaIII (1)) and Na24[Ln(H2O)8]2[(α2-P2W17O61H2)Ln(H2O)4]6·56H2O (Ln = CeIII (2), and PrIII (3)) have been successfully synthesized by straightforward “self assembly” processes starting from a 1:4 ratio of the saturated Dawson precursor [α-P2W18O62]6− and Ln ions in aqueous solution, which were further characterized by elemental analyses, X-ray powder diffraction (XRPD), IR spectra, thermogravimetric (TG) analyses, electrospray ionization mass spectrometry (ESI-MS) and single-crystal X-ray diffraction. The common feature of 1–3 is that they all consist of the trimeric triangular [(α2-P2W17O61)Ln(H2O)4]321− subunit, as we know, the trimeric [(α2-P2W17O61)Ln(H2O)4]321− polyoxoanion is firstly discovered. Furthermore, all three compounds can further generate three dimensional channel architectures through Na+ cations. Meanwhile, the multinuclear solution 31P NMR spectrum of 1 at 300 K in D2O has been investigated, the results are further demonstrated by the technologies of ESI-MS.
Co-reporter:Yanmei Zhou, Junli Zhang, Lin Zhang, Qingyou Zhang, Tongsen Ma, Jingyang Niu
Dyes and Pigments 2013 Volume 97(Issue 1) pp:148-154
Publication Date(Web):April 2013
DOI:10.1016/j.dyepig.2012.12.006
A rhodamine-based chemosensors (RF) was designed, and their sensing behavior toward metal ions was investigated by fluorescence spectroscopies. RF showed high selective recognition toward Cr3+ over other examined metal ions in aqueous media. With the optimum condition described, the response was linearly proportional to the concentration of Cr3+ in the range 0–10 μM with a detection limit of 0.023 μM. The proposed method was also applied to intracellular Cr3+ imaging in living cells and determination Cr3+ in tap water, river water.Graphical abstractHighlights► This work designed and synthesized a new fluorescent probe (RF). ► The probe showed high selectivity for Cr3+ in Tris–HCl (pH = 7.2) aqueous buffer solution. ► Possible response mechanism of RF and Cr3+ has preliminary studied as well. ► The probe was successful applied to intracellular Cr3+ imaging in living cells. ► The proposed method was also applied to determination Cr3+ in water samples.
Co-reporter:Lu Yang, Zhen Zhou, Pengtao Ma, Jingping Wang, and Jingyang Niu
Crystal Growth & Design 2013 Volume 13(Issue 6) pp:2540-2547
Publication Date(Web):April 18, 2013
DOI:10.1021/cg400292g
Two hybrid organic–inorganic organobisphosphonate polyoxomolybdates, Na4H2[(Mo3O8)2(O){O3PC(O)(CH2-3-C5NH5)PO3}2]·12H2O (1) and Na8[(Mo3O8){O3PC(O)(CH2-3-C5NH5)PO3}]4·30H2O (2), have been successfully synthesized and structurally characterized. Compounds 1 and 2 are prepared in aqueous solution by one-pot reaction of 1-hydroxo-2-(3-pyridyl) ethylidenebisphosphonate (risedronic acid) with molybdate. Structural analysis reveals that the two polyanions are composed of the same building blocks and can be described as a dimeric and tetrameric assembly of [(Mo3O8){O3PC(O)(CH2-3-C5NH5)PO3}]2– subunits, respectively. Elemental analysis, IR spectra, thermogravimetric analysis, and luminescence properties of the compounds have been studied in the solid state. The compounds are also characterized in the solution by multinuclear 31P NMR spectrometry, which evidences a subtle equilibrium between some species, and the results indicate that 1 presents two conformers of these hexanuclear polyanions in solution, whereas 2 is metastable, which might gradually decompose into one isomer of the dimer units. The photochromic property of 1 is determined under ultraviolet (UV) irradiation of 365 nm, and the sample develops a reddish coloration.
Co-reporter:Lei Yang, Xiang Ma, Pengtao Ma, Jiai Hua, and Jingyang Niu
Crystal Growth & Design 2013 Volume 13(Issue 7) pp:2982-2989
Publication Date(Web):May 15, 2013
DOI:10.1021/cg4004033
A series of arsenotungstates formulated as (H2en)3.5[HAs2W8O31]·6H2O (1), Na0.5(H2en)6.5{Ni3(en)[B-α-AsW9O34][B-β-AsW8O31]}Cl1.5·9H2O (2), and [H2en]4{[Ni4(Hen)2][B-α-AsW9O34]2}·5H2O (3) have been sequentially synthesized by controlling the reaction process. First, 1 was synthesized in an aqueous medium by the reaction of NiCl2 and NaAsO2 with Na2WO4, then colorless crystals of 1 transformed to yellow-green crystals of 2 for the further development of slow solvent evaporation, and, finally, yellow crystals of 3 generated over a sufficiently long time of solvent evaporation. 3 can also be hydrothermally synthesized in three different routes. Notably, 1 presents a [HAs2W8O31]7– building block, 2 exhibits an asymmetric sandwich-type arsenotungstate encapsulating two nonequivalent Keggin fragments [B-α-AsW9O34]9– and [B-β-AsW8O31]9–, and 3 is composed of two [B-α-AsW9O34]9– units sandwiching a tetranickel cluster. Their structural difference indicates that controlling the reaction process plays a key role in the structures and topologies of these complexes
Co-reporter:Jingjing Wei, Lu Yang, Pengtao Ma, Jingping Wang, and Jingyang Niu
Crystal Growth & Design 2013 Volume 13(Issue 8) pp:3554-3560
Publication Date(Web):July 10, 2013
DOI:10.1021/cg400536e
A series of novel lanthanide-containing peroxo-isopolyoxomolybdates, Na2(NH4)3[H3Ln6(H2O)26(MoO4){Mo7O22(O2)2}4]·nH2O [n = 24; Ln = CeIII (1), PrIII (2), SmIII (3), EuIII (4); n = 25; Ln = NdIII (5)] and Na4(NH4)3[H4La5(H2O)21(MoO4){Mo7O22(O2)2}4]·17H2O (6) have successfully been synthesized by the conventional method and further characterized by elemental analyses, X-ray photoelectron spectroscopy, X-ray powder diffraction, IR and UV spectra, thermogravimetric analyses, and single-crystal X-ray diffraction. All of the six compounds are composed of the [Ln4(H2O)16(MoO4){Mo7O22(O2)2}4]14– polyoxoanion. 1–5 can further generate two-dimensional structures through LnIII cations, whereas 6 shows the one-dimensional chain structure linked by LaIII cations. These compounds represent the first examples of introducing peroxo groups into the lanthanide-containing isopolyoxomolybdates. 1 is selected as an example to investigate the electrochemical behavior of these compounds. In addition, the fluorescence analyses of 3 and 4 have been studied. The spectra exhibit obvious fluorescence signals of SmIII and EuIII cations.
Co-reporter:Junwei Zhao, Dongying Shi, Lijuan Chen, Pengtao Ma, Jingping Wang, Jian Zhang, and Jingyang Niu
Crystal Growth & Design 2013 Volume 13(Issue 10) pp:4368-4377
Publication Date(Web):August 13, 2013
DOI:10.1021/cg400746n
Two novel 1D copper-bridged tetrahedral polyoxometalate nanoclusters with tetrameric rare-earth cores and germanotungstate vertexes, Na3H7[Cu(en)2]5[Cu(en)2(H2O)]2[RE4Ge4W46O164(H2O)3]·nH2O (RE = GdIII, n = 25 for 1; RE = YIII, n = 23 for 2; en = ethylenediamine), have been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectra, thermogravimetric analysis (TGA), and single-crystal X-ray diffraction. The most prominent structural feature of 1 and 2 consists of unprecedented tetrahedral RE-substituted germanotungstate nanoclusters {[(α-GeW11O39RE)2(μ3-WO4)(α-GeW11O39RE(H2O))](μ4-WO4)[α-GeW11O39RE(H2O)2]}24–, in which four mono-REIII-substituted Keggin [α-GeW11O39RE(H2O)n]5– (n = 0, 1, 2) moieties are combined together with the aid of two WO42– connectors. What’s more interesting is that adjacent tetrahedral nanoclusters are interconnected with each other via [Cu(en)2]2+ bridges, forming a 1D extended chain architecture. To our knowledge, 1 and 2 are the first polyoxometalate-based Cu–RE containing 1D chain constructed from tetrahedral RE-substituted germanotungstate nanoclusters and copper–organic bridges. Furthermore, the solid-state electrochemical and electrocatalytic properties of 1 and 2 have been carried out in 0.5 mol·L–1 Na2SO4 + H2SO4 aqueous solution by entrapping them in a carbon paste electrode. 1 and 2 display apparent electrocatalytic activities for the nitrite and bromate reduction.
Co-reporter:Yanmei Zhou, Xiaoyi Hu, Min Zhang, Xiaofeng Zhuo, and Jingyang Niu
Industrial & Engineering Chemistry Research 2013 Volume 52(Issue 2) pp:876
Publication Date(Web):December 26, 2012
DOI:10.1021/ie301742h
A novel absorbent composed of cellulose with thiosemicarbazide was prepared for the sorption of heavy metal ions and organic dyes from aqueous solutions. Cellulose was grafted with the vinyl monomer glycidyl methacrylate using ceric ammonium nitrate as initiator and was further functionalized with thiosemicarbazide to afford chemically modified cellulose (CMC). CMC was characterized with FTIR, SEM, TGA, XPS, and XRD. In this work, CMC was used for the adsorption of Hg(II), Cd(II), and acid fuchsin (AF) from their aqueous solutions. The effects of varying parameters such as pH, contact time, temperature, and initial concentration on the adsorption process were examined. According to the obtained results, the adsorption processes could be described by a pseudo-second-order kinetic model. Langmuir, Freundlich, and Temkin adsorption isotherm models were applied to describe isotherm constants. Cd(II) and AF equilibrium data agreed well with the Langmuir isotherm model, while Hg(II) equilibrium data exhibited a better fit to the Temkin isotherm model.
Co-reporter:Lu Li, Pengtao Ma, Jingping Wang, Jingyang Niu
Inorganic Chemistry Communications 2013 Volume 34() pp:23-26
Publication Date(Web):August 2013
DOI:10.1016/j.inoche.2013.04.007
•Saturated Wells–Dawson phosphomolybdate•Inorganic TM-containing phosphomolybdates•6–connected 2–D topological networkA novel compound based on saturated Wells–Dawson type phosphomolybdate, [Cu(H2O)4]3[P2Mo18O62]·12H2O (1) has been synthesized by the conventional solution method and characterized by elemental analysis, IR spectrum, UV spectrum, thermogravimetric analysis, electrospray ionization mass spectrometry (ESI-MS), electrochemistry and single-crystal X-ray diffraction. X-ray structural analysis reveals that 1 exhibits the 6-connected 2D topological network with the Schläfli symbol of (3649).A novel compound based on saturated Well-Dawson type phosphomolybdates [Cu(H2O)4]3[P2Mo18O62]·12H2O (1) which exhibits a 2D network constructed from [P2Mo18O62]6– interconnected through [Cu(H2O)4]2+ bridging, has been synthesized by the conventional solution method. 1 exhibits the electrochemical behavior.
Co-reporter:Xiang Ma, Jiai Hua, Pengtao Ma, Lei Yang, Jingping Wang, Jingyang Niu
Journal of Molecular Structure 2013 Volume 1047() pp:9-14
Publication Date(Web):5 September 2013
DOI:10.1016/j.molstruc.2013.04.060
•The title compound represents the first 2-D network Zn-substituted sandwich-type tungstoarsenate.•The title compound has been synthesized by combining the conventional aqueous solution method and the hydrothermal method.•Two ZnII ions in the Zn4 cluster are coordinated by the monoprotonated [Hdap]+ ligand in the end-on coordination fashion.•The interesting phenomenon of photoluminescence may contribute to the researches on POM.A new 2-D network tetra-ZnII-substituted sandwich-type Keggin tungstoarsenate {[Zn(dap)2(H2O)]2[Zn(dap)2]2[Zn4(Hdap)2(B-α-AsW9O34)2]}·4H2O (1) (dap = 1,2-diaminopropane) has been synthesized by combining the conventional aqueous solution method and the hydrothermal method and structurally characterized by elemental analyses, X-ray powder diffraction (XRPD), IR spectrum, thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. Structural analysis shows that 1 displays an interesting 2-D (4,4)-topological network constructed by tetra-ZnII-substituted sandwich-type Keggin tungstoarsenate units and [Zn(dap)2)2+] linkers. To our knowledge, 1 represents the first 2-D network Zn-substituted sandwich-type tungstoarsenate. The fluorescent properties of 1 have also been investigated.
Co-reporter:Qiuxia Han, Hongxia Cao, Pengtao Ma, Junwei Zhao, Jingyang Niu
Inorganic Chemistry Communications 2013 Volume 28() pp:7-11
Publication Date(Web):February 2013
DOI:10.1016/j.inoche.2012.11.004
An organic–inorganic hybrid 1D helical chain arsenomolybdate {[Cu(en)2][Cu(en)(H2O)][(Cu(en)2(H2O)] [AsIIIAsVMo9O34)]} · 2H2O (1) (en = ethylenediamine) has been hydrothermally synthesized and characterized by elemental analyses, IR, UV and CD spectrum, powder X-ray diffraction, TG-DTA and single-crystal X-ray diffraction. The asymmetric unit of 1 consists of a monocapped trivacant Keggin [AsIIIAsVMo9O34]6 − subunit, a pendant [Cu(en)2(H2O)]2 + cation, a pendant [Cu(en)(H2O)]2 + cation, one bridging [Cu(en)2]2 + cation and two lattice water molecules. It should be noted that 1 illustrates a one-dimensional (1D) helical chain assembled by {[Cu(en)(H2O)][(Cu(en)2(H2O)][AsIIIAsVMo9O34)]}2 − clusters and [Cu(en)2]2 + linkers.A new organic–inorganic hybrid arsenomolybdate {[Cu(en)2][Cu(en)(H2O)][(Cu(en)2(H2O)] [AsIIIAsVMo9O34)]} · 2H2O has been hydrothermally synthesized, which displays a 1D helical chain assembled from {[Cu(en)(H2O)][(Cu(en)2(H2O)][AsIIIAsVMo9O34)]}2 − clusters and [Cu(en)2]2 + linkers.Highlights► Reports on TM-containing lacunary arsenomolybdate fragments are rather rare. ► A novel organic–inorganic arsenomolybdate hybrid was hydrothermally obtained. ► The first hybrid assembled from [AsIIIAsVMo9O34)]} clusters and {Cu(en)2} linkers ► The hybrid displays a unique 1D helical chain.
Co-reporter:Jie Luo, Junwei Zhao, Jing Yuan, Yanzhou Li, Lijuan Chen, Pengtao Ma, Jingping Wang, Jingyang Niu
Inorganic Chemistry Communications 2013 Volume 27() pp:13-17
Publication Date(Web):January 2013
DOI:10.1016/j.inoche.2012.10.014
An organic–inorganic hybrid 1-D double-chain CuII–YIII heterometallic silicotungstate [Cu(dap)2(H2O)]2 {Cu(dap)2[α-H2SiW11O39Y(H2O)2]2}·10H2O (1) has been synthesized by reaction of Na10[A-α-SiW9O34]·18H2O, CuCl2·2H2O, YCl3 and dap (dap = 1,2-diaminopropane) under hydrothermal conditions and characterized by elemental analyses, IR spectrum, UV spectrum and single-crystal X-ray diffraction. 1 exhibits a novel 1-D double-chain structure constructed from dimeric CuII–YIII heterometallic silicotungstate units. To our knowledge, 1 is the first organic–inorganic hybrid 1-D double-chain CuII–YIII heterometallic polyoxometalate. Thermogravimetry-differential thermal analysis of 1 has been measured from 25 to 750 °C and the thermogravimetric curve indicates two steps of weight loss.Graphical abstractA 1-D double-chain CuII–YIII heterometallic silicotungstate [Cu(dap)2(H2O)]2{Cu(dap)2[α-H2SiW11O39Y(H2O)2]2}·10H2O has been synthesized and is the first organic–inorganic hybrid 1-D double-chain CuII–YIII heterometallic polyoxometalate.Highlights► copper–yttrium heterometallic silicotungstate ► 1-D double-chain structure ► hybrid 1-D double-chain CuII–YIII heterometallic polyoxometalate ► POM-based TM–RE heterometallic derivatives
Co-reporter:Lu Yang, Pengtao Ma, Xiaoqing Zhang, Jingyang Niu, Jingping Wang
Inorganic Chemistry Communications 2013 Volume 35() pp:5-8
Publication Date(Web):September 2013
DOI:10.1016/j.inoche.2013.05.005
A novel Dy(III)-based organodiphosphonate-functionalized polyoxomolybdate [NH2(CH3)2]3{[Dy(DMF)2(H2O)4]3[Dy(DMF)3{(Mo3O8)(O3PCOCH3PO3)}3]2}∙6DMF·2H2O (1) (DMF = N,N-Dimethylformamide) has been synthesized and characterized by elemental analysis, IR spectrum, thermogravimetric analysis (TG), UV spectroscopy, fluorescence spectroscopy and single-crystal powder X-ray diffraction (PXRD). Compound 1 is composed of two monocapped [Dy(DMF)3{(Mo3O8)(O3PCOCH3PO3)}3]6 − subunits and three [Dy(DMF)2(H2O)4]3 + coordination cations, which contain an internal capsule. The UV spectra indicate that compound 1 is stable in the pH range of 2.76–4.75.A novel Dy(III)-based organodiphosphonate-functionalized polyoxomolybdate [NH2(CH3)2]3{[Dy(DMF)2(H2O)4]3[Dy(DMF)3((Mo3O8)(O3PCOCH3PO3))3]2}∙6DMF·2H2O has been successfully synthesized. The polyanion displays a cage-like structure, which is constructed from two monocapped [Dy(DMF)3((Mo3O8)(O3PCOCH3PO3))3]6 − fragments and three [Dy(DMF)2(H2O)4]3 + subunits.Highlights•Lanthanide-containing organodiphosphonate-functionalized polyoxomolybdates are rare.•A Dy(III)-based polyoxomolybdate constructed by HEDP ligand was obtained.•The hybrid compound 1 displays a unique cage-like structure.•The UV spectra indicate that 1 is stable in a certain pH range.
Co-reporter:Dongdi Zhang, Chunzhang Wang, Suzhi Li, Jiangping Liu, Pengtao Ma, Jingping Wang, Jingyang Niu
Journal of Solid State Chemistry 2013 Volume 198() pp:18-23
Publication Date(Web):February 2013
DOI:10.1016/j.jssc.2012.09.013
Interaction of the lacunary [α-SbW9O33]9– with Fe3+ in the presence of organic amines under hydrothermal conditions yields two novel inorganic–organic hybrid tungstoferrites [dapH2]3[enH2][enH]Na[Fe4(H2O)2(FeW9O34)2]·7H2O (dap=1,2-diaminopropane, en=ethylenediamine) (1) and [dapH2]5[Fe4(H2O)2(FeW9O34)2]·11H2O (2), which have been characterized by IR, elemental analysis, UV–Vis, TG and single-crystal X-ray diffraction. Both 1 and 2 consist of two [B-α-FeIIIW9O34]11− units joined by a rhomb-like tetranuclear iron cluster. Interestingly, 1 displays a new example of 1D chain-like architecture, in which adjacent [Fe4(FeW9O34)2]10– anions are interconnected by two unusual W–O–Fe bridges. Meanwhile, the neighboring chains are further assembled by Na+ ions, forming the 2D extended network. 2 exhibits a discrete dimeric TMSP structure constructed from two trivacant [B-α-FeIIIW9O34]11− subunits encapsulating a rhomb-like tetranuclear iron cluster with five isolated diprotoned dap molecules. Magnetic measurements indicate that antiferromagnetic exchange interactions are dominant in the hexanuclear {Fe6O22} clusters in 1 and 2.Graphical abstractTwo novel inorganic–organic hybrid tungstoferrites were synthesized from the reaction of lacunary [α-SbW9O33]9– with Fe3+ under hydrothermal conditions and structurally characterized. The magnetic properties of them were also studied. Highlights► 1 represents the first example of 1D chain-like {Fe4(FeW9)2} tungstoferrite. ► Two [B-α-FeIIIW9O34]11− units linked via a rhomb-like tetranuclear iron cluster. ► Adjacent {Fe4(FeW9)2} are interconnected by unusual WOFe bridges. ► Antiferromagnetic exchange interactions are dominant in the {Fe6O22} cluster.
Co-reporter:Yanmei Zhou, Min Zhang, Xiaoyi Hu, Xinhai Wang, Jingyang Niu, and Tongsen Ma
Journal of Chemical & Engineering Data 2013 Volume 58(Issue 2) pp:413-421
Publication Date(Web):January 9, 2013
DOI:10.1021/je301140c
A novel adsorbent based on cellulose (CGD) was prepared via modifying with glycidyl methacrylate (GMA) and diethylenetriamine pentaacetic acid (DTPA), characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and differential thermogravimetry (DTA/TGA). Malachite green (MG) and basic fuchsine (BF) were used to resemble cationic dyes in wastewaters. The influences of several parameters (contact time, pH, temperature, initial concentration) were evaluated to determine the best adsorption conditions. Langmuir adsorption isotherm items explained MG adsorption well, while BF was fitted well with the Freundlich model. The maximum adsorption capacities were greater than some other reports, 1155.76 mg·g–1 for a BF internal concentration of 2000 mg·L–1 and 458.72 mg·g–1 for MG in theory. Kinetics and thermodynamics were adopted to explain in-depth information associated with the adsorption process. The adsorption processes of dyes were both feasible spontaneous and well-described by the pseudosecond-order model. The dynamic adsorption/desorption experiments, with saturated sodium bicarbonate solution as the eluent, show that the adsorbent could be reused for five cycles or four cycles, keeping the adsorption rate above 85 % and 90 % for BF and MG, respectively.
Co-reporter:Junli Zhang;Lin Zhang;Yanmei Zhou;Tongsen Ma;Jingyang Niu
Microchimica Acta 2013 Volume 180( Issue 3-4) pp:211-217
Publication Date(Web):2013 February
DOI:10.1007/s00604-012-0922-2
We report on a fluorescent probe for the optical (and even bare eye) detection of palladium(II) ion which causes the probe to undergo a strong increase in absorbance and fluorescence. The probe is easily synthesized from rhodamine B hydrazide and 9-anthraldehyde and displays high selectivity over other metal ions. Fluorescence intensity and absorbance are linearly proportional to the concentration of Pd(II) in the 0–7 μM and 0–1 μM concentration range, respectively, with detection limits of 0.21 μM and 0.03 μM. The probe can detect Pd(II) with virtually no interferences by other metal ions and anions. It was applied to intracellular imaging of Pd(II) in living cells and to its determination in a palladium-containing catalyst and in spiked water samples.
Co-reporter:Jiai Hua;Xiang Ma;Pengtao Ma;Jingping Wang;Jingyang Niu
Journal of Cluster Science 2013 Volume 24( Issue 3) pp:689-700
Publication Date(Web):2013 September
DOI:10.1007/s10876-012-0536-1
A new compound H8[NaCu5Cl(H2O)3(B-α-AsW9O33)2] 24H2O (1) is synthetized by the reaction of the CuCl2 2H2O and Na27[NaAs4W40O140] 60H2O in aqueous solution, which is constructed from a {Cu5Na} hexagon moiety sandwiched by two trilacunary [B-α-AsW9O33]9− units. The structure is determined by single-crystal X-ray diffraction technique and further characterized by IR spectroscopy. Single-crystal X-ray diffraction analysis reveals that 1 is built by two trilacunary [B-α-AsW9O33]9− units incorporating a {Cu5Na} hexagon moiety and further linked to each other to form an infinitely extended 2-D network via Cu–O–W bridges. Notably, magnetic measurement demonstrates that the occurrence of intramolecular ferromagnetic Cu–Cu interactions within {Cu5Na} hexagon moiety.
Co-reporter:Suzhi Li, Dongdi Zhang, Yuan Yuan Guo, Pengtao Ma, Xiaoyang Qiu, Jingping Wang and Jingyang Niu
Dalton Transactions 2012 vol. 41(Issue 33) pp:9885-9888
Publication Date(Web):23 May 2012
DOI:10.1039/C2DT30517H
A novel strawberry-like organic–inorganic hybrid, {Na(H2O)3[Lu(pydc)(H2O)3]3}[SiW12O40]·26.5H2O (H2pydc = pyridine-2,6-dicarboxylate) containing an intriguing trinuclear lutetium cluster {Na(H2O)3[Lu(pydc)(H2O)3]3}4+ has been synthesized and its luminescent properties, IR, UV, TG, PXRD analyses and single crystal X-ray diffraction were investigated.
Co-reporter:Juan Zhao, Junsheng Wang, Junwei Zhao, Pengtao Ma, Jingping Wang and Jingyang Niu
Dalton Transactions 2012 vol. 41(Issue 19) pp:5832-5837
Publication Date(Web):26 Mar 2012
DOI:10.1039/C2DT12130A
Two novel trivacant Keggin-type polyoxometallate-based manganese carbonyl derivatives K8[(OC)3Mn(A-α-H2GeW9O34)]·10H2O (1) and K8[(OC)3Mn(A-α-H2SiW9O34)]·11H2O (2) have been synthesized by degradation of the metastable [γ-XW10O36]8− (X = GeIV, SiIV) in CH3CN–H2O solvent (1:2, vol.) and structurally characterized by elemental analyses, IR spectra, thermogravimetric analysis, and single-crystal X-ray diffraction. X-ray diffraction analyses indicate that 1 and 2 are isomorphic and consist of a [(OC)3Mn]+ group and a trivacant [A-α-H2XW9O34]8− fragment, which exhibit the first examples of trivacant Keggin-type metal carbonyl derivatives. Additionally, the electrocatalytic properties of both for NO2− oxidation have been investigated.
Co-reporter:Suzhi Li, Yuan yuan Guo, Dongdi Zhang, Pengtao Ma, Xiaoyang Qiu, Jingping Wang and Jingyang Niu
Dalton Transactions 2012 vol. 41(Issue 17) pp:5235-5240
Publication Date(Web):20 Feb 2012
DOI:10.1039/C2DT12491B
Four di-CuII-substituted sandwich-type germanomolybdates, (H2en)2H7{[Na0.5(H2O)3.5]2[Cu2(β-Y-GeMo9O33)2]}·6H2O (1), (H2en)2H{[Na2.5(H2O)12]2[Cu(en)2][Cu2(β-Y-GeMo9O33)2]}·8H2O (2), [Na4(H2O)12]2H4[Cu2(β-Y-GeMo9O33)2]}·11H2O (3) and [Cu(en)2]2[Cu(en)2(H2O)]2{[Cu(en)2]2[Cu2(β-Y-GeMo9O33)2]}·8H2O (4) (en = ethylenediamine), have been prepared. It is interesting that 1–3 were obtained in the same aqueous solution reaction system but exhibited different structures: 1 displays a 0D structure, 2 shows an organic–inorganic 1D chain structure, while 3 displays a 2D network. 4 was synthesized under hydrothermal condition by the same reagents, which represents the first transition metal-sandwiched organic–inorganic 2D heteropolymolybdate.
Co-reporter:Shaowei Zhang, Ke Wang, Dongdi Zhang, Pengtao Ma, Jingyang Niu and Jingping Wang
CrystEngComm 2012 vol. 14(Issue 24) pp:8677-8683
Publication Date(Web):09 Oct 2012
DOI:10.1039/C2CE26208H
Seven organic–inorganic hybrid lanthanide dimolybdates [Ln(H2O)6Mo2O6(Hpydc)(pydc)]·nH2O (n = 0: Ln = LaIII (1), CeIII (2), PrIII (3), NdIII (4), SmIII (5); n = 0.5: Ln = EuIII (6)), and Na0.5H0.5[Er(H2O)5Mo2O6(pydc)2]·3H2O (7) (H2pydc = pyridine-2,5-dicarboxylic acid) have been hydrothermally prepared and further characterized by elemental analyses, X-ray powder diffraction (XRPD), IR spectra, thermogravimetric (TG) analyses, and single-crystal X-ray diffraction. The common feature of 1–7 is that they all consist of LnIII cations and MoIV centers connected by oxygen atoms and H2pydc ligands. 1–6 show unprecedented 3D 8-connected networks with the Schläfli symbol of (34·417·54·63), while 7 exhibits the 2D 4-connected (45·6) structure. Furthermore, the luminescence properties of 5 and 6 are derived from the combination of Ln cations and H2pydc ligands, whereas 1–4 and 7 are attributable to H2pydc ligands.
Co-reporter:Junwei Zhao, Jie Luo, Lijuan Chen, Jing Yuan, Huiying Li, Pengtao Ma, Jingping Wang and Jingyang Niu
CrystEngComm 2012 vol. 14(Issue 23) pp:7981-7993
Publication Date(Web):24 Aug 2012
DOI:10.1039/C2CE26007G
A series of novel 1-D double-chain organic–inorganic hybrid polyoxotungstates [Cu(dap)2(H2O)]2{Cu(dap)2[α-H2SiW11O39Ln(H2O)3]2}·xH2O [Ln = CeIII, x = 9 (1); Ln = PrIII, x = 10 (2), Ln = NdIII, x = 10 (3), Ln = SmIII, x = 10 (4), Ln = EuIII, x = 10 (5), Ln = GdIII, x = 9 (6), Ln = TbIII, x = 8 (7), Ln = DyIII, x = 8 (8), Ln = ErIII, x = 9 (9)] (dap = 1,2-diaminopropane) have been hydrothermally prepared and structurally characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry, IR spectra, UV-Vis spectra, thermogravimetric analyses and single-crystal X-ray diffraction. Compounds 1–9 are isomorphic and display the novel 1-D double-chain built by dimeric copper–lanthanide heterometallic silicotungstate units by means of the bridging role of the lanthanide cations, to our knowledge, which represent the first organic–inorganic hybrid 1-D double-chain copper–lanthanide heterometallic polyoxometalates. The variable-temperature magnetic susceptibilities of 2, 3, 6 and 8 have been investigated. The solid-state photoluminescence properties of 4, 5, 7 and 8 have been measured at room temperature.
Co-reporter:Dong-Ying Shi, Jun-Wei Zhao, Li-Juan Chen, Peng-Tao Ma, Jing-Ping Wang and Jing-Yang Niu
CrystEngComm 2012 vol. 14(Issue 9) pp:3108-3119
Publication Date(Web):24 Feb 2012
DOI:10.1039/C2CE06354A
Four types of organic–inorganic hybrids Na[Cu(en)2(H2O)]4[Cu(en)2]2[Cu(H2O)4]0.5{Cu(en)2[H2CeIV(α-AsW11O39)2]2}·10H2O (1), Na3[Cu(en)2(H2O)][Cu(en)2]1.5[H3Ln(α-AsW11O39)2]·xH2O [Ln = PrIII, x = 5 (2); Ln = NdIII, x = 4.5 (3); Ln = SmIII, x = 5.5 (4); Ln = EuIII, x = 4 (5); Ln = TbIII, x = 4 (6)], [Cu(dap)(H2O)2]0.5[Cu(dap)2(H2O)]2[Cu(dap)2]3[Ln(α-AsW11O39)2]·xH2O [Ln = PrIII, x = 3 (7); Ln = EuIII, x = 3 (8)] and [Cu(dap)2]5.5[Ln(α-AsW11O39)2]·xH2O [Ln = TbIII, x = 6 (9); Ln = DyIII, x = 5 (10)] (en = ethylenediamine, dap = 1,2-diaminopropane) have been hydrothermally synthesized and fully characterized by elemental analyses, IR spectra, solid-state UV spectra, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. 1 exhibits the first 2D TM–Ln heterometallic sheet architecture with a 4-connected topology established by tetrameric [Cu(H2O)4{Cu(en)2[H2Ce(α-AsW11O39)2]2}2]26− units via [Cu(en)2]2+ bridges. 2–6 are isomorphic and display the unique 2D (6,3)-network topology constructed from 1:2-type [H3Ln(α-AsW11O39)2]8− units through [Cu(en)2]2+ linkers. 7–8 represent the first 1D “dendritic” chain-like TM–Ln heterometallic POMs based on the 1:2-type [Ln(α-AsW11O39)2]11− units. 9–10 are the unique 2D sheets built by 1:2-type [Ln(α-AsW11O39)2]11− units and [Cu(dap)2]2+ connectors, in which the [Ln(α-AsW11O39)2]11− subunits act as 5-connected nodes and adjacent 2D sheets are packed in the mode of –AAA–. The photocatalytic measurements show that 1–10 can to some extent inhibit the photodegradation of rhodamine-B (RhB). Moreover, the luminescence properties of 5–6 and 8–9 have been investigated.
Co-reporter:Junwei Zhao, Dongying Shi, Lijuan Chen, Xiaomeng Cai, Zhiqiao Wang, Pengtao Ma, Jingping Wang and Jingyang Niu
CrystEngComm 2012 vol. 14(Issue 8) pp:2797-2806
Publication Date(Web):07 Feb 2012
DOI:10.1039/C2CE06298D
Two organic–inorganic hybrid hexa-CuII substituted sandwich-type arsenotungstates [Cu(en)2(H2O)]2 [Cu(en)2][Cu6(en)2(H2O)2(B-α-AsW9O34)2]·en·9H2O (1) and [Cu(dap)2]3[Cu6(dap)2(H2O)2(B-α-AsW9O34)2]·4H2O (2) (en = ethylenediamine, dap = 1,2-diaminopropane) have been hydrothermally prepared and structurally characterized by elemental analysis, IR spectra, powder X-ray diffraction (XRD), thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. 1 is an organic–inorganic hybrid 1-D chain constructed from hexa-CuII substituted [Cu6(en)2(H2O)2(B-α-AsW9O34)2]6− sandwich-type units and [Cu(en)2]2+ linkers whereas 2 shows the six-connected 3-D extended framework built by hexa-CuII sandwiched [Cu6(dap)2(H2O)2(B-α-AsW9O34)2]6− units and [Cu(dap)2]2+ connectors. To our knowledge, 1 and 2 represent the first organic–inorganic hybrid high-dimensional arsenotungstates containing hexa-CuII sandwiched polyoxometalate units. The results of magnetic susceptibility measurements demonstrate that 1 and 2 indicates the ferromagnetic couplings within CuII centers. The photocatalytic measurements illustrate that 1 and 2 can to some extent inhibit the photodegradation of rhodamine-B (RhB).
Co-reporter:Yan Bai, Jun-Li Wang, Dong-Bin Dang, Meng-Meng Li and Jing-Yang Niu
CrystEngComm 2012 vol. 14(Issue 5) pp:1575-1581
Publication Date(Web):15 Dec 2011
DOI:10.1039/C1CE06030A
Four new inorganic–organic hybrid coordination polymers {[Ag2L(NO3)2]·H2O}n (1), [Ag2L(SCN)2]n (2), [CdL(SCN)2]n (3), and [CdLI2]n (4) have been synthesized and structurally characterized by IR spectroscopy, thermogravimetric (TG) analyses and complete single crystal structure analyses, where L is 2,5-bis(pyrazinyl)-3,4-diaza-2,4-hexadiene. The structure of polymer 1 is a 3D coordination framework containing Ag-(μ-NO3−) inorganic bridging units, in which each L coordinates four silver atoms through two pyrazinylimine chelate units and two terminal monodentate pyrazinyl N donors. Polymer 2 displays a new 3D inorganic–organic hybrid network through the coordination interactions between Ag-(1,1,3-μ-SCN−) inorganic 2D sheets and bidentate bridging ligands with two terminal monodentate pyrazinyl N donors. Bidentate bridging ligands link 1D inorganic chains Cd-(1,3-μ-SCN−) system for 3 and Cd-(μ-I−) system for 4 to form a similar two-dimensional layer network. The luminescent properties of polymers 1–4 were investigated in the solid state at room temperature.
Co-reporter:Junwei Zhao, Dongying Shi, Lijuan Chen, Yanzhou Li, Pengtao Ma, Jingping Wang and Jingyang Niu
Dalton Transactions 2012 vol. 41(Issue 35) pp:10740-10751
Publication Date(Web):17 Jul 2012
DOI:10.1039/C2DT30949A
Three organic–inorganic hybrid copper–lanthanide heterometallic germanotungstates, {[Cu(en)2(H2O)] [Cu3Eu(en)3(OH)3(H2O)2](α-GeW11O39)}2·11H2O (1), {[Cu(en)2(H2O)][Cu3Tb(en)3(OH)3(H2O)2](α-GeW11O39)}2·11H2O (2) and {[Cu(en)2(H2O)][Cu3Dy(en)3(OH)3(H2O)2](α-GeW11O39)}2·10H2O (3) and three polyoxometalate hybrids built by lanthanide-containing germanotungstates and copper–ethylendiamine complexes, Na2H6[Cu(en)2(H2O)]8{Cu(en)2[La(α-GeW11O39)2]2}·18H2O (4), K4H2[Cu(en)2(H2O)2]5[Cu(en)2(H2O)]2[Cu(en)2]2{Cu(en)2[Pr(α-GeW11O39)2]2}·16H2O (5) and KNa2H7[enH2]3[Cu(en)2(H2O)]2[Cu(en)2]2{Cu(en)2[Er(α-GeW11O39)2]2}·15H2O (6) (en = ethylenediamine) have been hydrothermally synthesized and structurally characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP–AES) analyses, IR spectra, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS) and single-crystal X-ray diffraction. 1–3 are essentially isomorphous and their main skeletons display the interesting dimeric motif {[Cu3Ln(en)3(OH)3(H2O)2](α-GeW11O39)}24−, which is constructed from two {Cu3LnO4} cubane anchored monovacant [α-GeW11O39]8− fragments through two W–O–Ln–O–W linkers. The primary backbones of 4–6 exhibit the tetrameric architecture {Cu(en)2[Ln(α-GeW11O39)2]2}24− built by two 1:2-type [Ln(α-GeW11O39)2]13− moieties and one [Cu(en)2]2+ bridge, albeit they are not isostructural. To our knowledge, 1–6 are rare polyoxometalate derivatives consisting of copper–lanthanide heterometallic/lanthanide germanotungstate fragments. 1 exhibits antiferromagnetic coupling interactions within the {Cu3EuO4} cubane units, while 2 and 3 display dominant ferromagnetic interactions between the TbIII/DyIII and CuII cations. The room-temperature solid-state photoluminescence properties of 1–3 have been investigated.
Co-reporter:Shaowei Zhang, Junwei Zhao, Pengtao Ma, Huanni Chen, Jingyang Niu, and Jingping Wang
Crystal Growth & Design 2012 Volume 12(Issue 3) pp:1263-1272
Publication Date(Web):January 18, 2012
DOI:10.1021/cg2012759
A series of organic–inorganic hybrid lacunary Keggin silicotungstate 3d-4f heterometallic derivatives, {[Cu (en)2]1.5Ln[(α-SiW11O39)2]}220– [Ln = GdIII for 1, TbIII for 2, DyIII for 3, ErIII for 4, LuIII for 5], {[Cu(en)2]1.5Ln[(α-SiW11O39)]}2– [Ln = LaIII for 6, CeIII, for 7] and {[Cu(en)2(H2O)][Cu(en)2]nLn[(α-SiW11O39)2]}m− [(Ln, n, m) = (PrIII, 2, 7) for 8, (SmIII, 3, 5) for 9] (en = ethylenediamine) have been successfully synthesized under hydrothermal conditions and further characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP-AES) analyses, X-ray powder diffraction (XRPD), IR spectra, thermogravimetric (TG) analyses, and single-crystal X-ray diffraction. The common features of 1–5 and 8–9 are that they all consist of a sandwich-type [Ln(α-SiW11O39)2]13– polyoxoanion, whereas both 6 and 7 consist of the unusual 1:1 [Ln(α-SiW11O39)]5– units and [Cu(en)2]2+ coordination cations. 1–5 show dimeric structures, and 6–9 display unprecedented three-dimensional (3D) frameworks, representing the first 3D 3d-4f heterometallic silicotungstates. The features of 6 and 7 are that the components are closely packed along the 21 screw axis to generate scarce 5-connected network structures with the Schläfli symbol of (48·62), while 8 and 9 exhibit the 4-connected (66) topology and 6-connected (48·54·63) topology structures, respectively. Furthermore, 2, 3, and 9 manifest apparent fluorescence signals, which can be assigned to the characteristic emissions of TbIII, DyIII, and SmIII cations, respectively.
Co-reporter:Dongbin Dang, Yanning Zheng, Yan Bai, Xiangyang Guo, Pengtao Ma, and Jingyang Niu
Crystal Growth & Design 2012 Volume 12(Issue 8) pp:3856-3867
Publication Date(Web):June 14, 2012
DOI:10.1021/cg300075a
Six crystalline polyoxometalate-based three-dimensional (3D) metal–organic frameworks {[AgL4(DMF)][AgL4]2(PMo12O40)·DMF·3H2O}n (1), {[AgL4]3(PW12O40)·6H2O}n (2), {[AgL5]3(PMo12O40)·(CH3CN)3}n (3), {[AgL5(PW12O40)][AgL5(H2O)0.25(MeOH)0.25)][AgL5]0.5·DMF·(H2O)1.5}n (4), {[AgL6]3(PMo12O40)·DMF·H2O}n (5), and {[AgL7]3(PMo12O40)·DMF·(CH3CN)3}n (6) have been successfully synthesized based on one-dimensional (1D) coordination polymers constructed by the coordination of polydentate Schiff-base ligands and silver cations and saturated α-Keggin polyoxoanion [PM12O40]3– (M = W, Mo) as building blocks, where L4, L5, L6, and L7 are 2,5-bis(3-pyridyl)-3,4-diaza-2,4-hexadiene, 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene, 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene, and 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, respectively. Compounds 1–6 are structurally characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses (TG), powder X-ray diffraction (XRD), and complete single-crystal X-ray diffraction analyses. The structures of 1–6 exhibit 3D supramolecular networks formed by linking 1D Ag-Schiff base chains and α-Keggin polyoxoanion units through the cooperativity of multiform supramolecular interactions, such as intermolecular Ag···O weak interactions, Ag···π interactions, π···π interactions, and hydrogen bonds. The photoluminescent properties of 1–6 have been investigated in the solid state.
Co-reporter:Ming Xue Li, Li Zhi Zhang, Chun Ling Chen, Jing Yang Niu, Bian Sheng Ji
Journal of Inorganic Biochemistry 2012 Volume 106(Issue 1) pp:117-125
Publication Date(Web):January 2012
DOI:10.1016/j.jinorgbio.2011.09.034
Two NNS tridentate Schiff base ligands of 2-benzoylpyridine S-methyldithiocarbazate (HL1) and 2-benzoylpyridine S-phenyldithiocarbazate (HL2) and their transition metal complexes [Cu2(L1)2(CH3COO)](ClO4) (1), [Zn2(L1)2(ClO4)2] (2), [Zn(L2)2](3) have been prepared and characterized by elemental analysis, IR, MS, NMR and single-crystal X-ray diffraction studies. In the solid state, each of two Schiff bases remains in its thione tautomeric form with the thione sulfur atom trans to the azomethine nitrogen atom. Under similar prepared conditions, three new complexes showed distinctly different coordination modes depending on their coordinating preferences. Each copper atom in S-bridged dinuclear complex [Cu2(L1)2(CH3COO)](ClO4) (1) is surrounded by five donor atoms in a square-pyramidal fashion (4 + 1). [Zn2(L1)2(ClO4)2] (2) is a dimer in which each zinc atom adopts a seven-coordinate distorted pentagonal bipyramidal geometry, while mononuclear [Zn(L2)2] (3) has octahedral coordination geometry. Biological studies, carried out in vitro against selected bacteria, fungi, and K562 leukaemia cell line, respectively, have shown that different substituted groups attached at the dithiocarbazate moieties and metals showed distinctive differences in the biological property. Zinc(II) complexes 2 and 3 could distinguish K562 leukaemia cell line from normal hepatocyte QSG7701 cell line. Effect of the title compounds on Mitochondria membrane potential (MMP) and PI-associated fluorescence intensity in K562 leukaemia cell line are also studied. The title compounds may exert their cytotoxicity activity via induced loss of MMP.Two NNS tridentate Schiff base ligands and their transition metal complexes have been synthesized and fully characterized. Under similar prepared conditions, three new complexes showed distinctly different coordination modes depending on their coordinating preferences. Biological studies have shown that different substituted groups attached at the dithiocarbazate moieties and metals showed distinctive differences in the biological property. Two zinc(II) complexes could distinguish K562 leukaemia cell line from normal hepatocyte QSG7701 cell line. The title compounds may exert their cytotoxic activity via induced loss of MMP.Highlights► Two Schiff base ligands and their complexes have been synthesized and characterized. ► Three new complexes showed distinctly different coordination modes. ► The tested compounds showed distinctive differences in the biological property. ► They may exert their cytotoxic activity via induced loss of MMP.
Co-reporter:Yanmei Zhou, Junli Zhang, Hua Zhou, Qingyou Zhang, Tongsen Ma, Jingyang Niu
Journal of Luminescence 2012 Volume 132(Issue 8) pp:1837-1841
Publication Date(Web):August 2012
DOI:10.1016/j.jlumin.2012.03.016
A new fluorescent probe 1 (P1) for Cu2+ based on rhodamine B was designed and synthesized. P1 exhibits high sensitivity and selectivity for sensing Cu2+ and color changes from colorless to pink in aqueous media. Selective fluorescent enhancement of P1 was attributed to ring-opening from the spirolactam (nonfluorescent) to ring-opened amide (fluorescent). A chemosensor based on rhodamine B has a good potential application to the determination of Cu2+ in environmental and biological systems.Highlights► This work designed and synthesized a new fluorescent probe (P1) based on rhodamine B derivative. ► The probe showed high selectivity for Cu2+ over other metal ions and color change from colorless to pink in aqueous solution. ► Based on the specific response of P1 toward Cu2+, a novel fluorescent probe for the determination of Cu2+ was developed.
Co-reporter:Ming-Xue Li, Li-Zhi Zhang, Min Yang, Jing-Yang Niu, Jing Zhou
Bioorganic & Medicinal Chemistry Letters 2012 Volume 22(Issue 7) pp:2418-2423
Publication Date(Web):1 April 2012
DOI:10.1016/j.bmcl.2012.02.024
Two metal complexes formulated as [Zn(L)2]2·H2O (1) and [Bi(L)(NO3)2(CH3OH)] (2), where HL = 2-acetylpyrazine N(4)-phenylthiosemicarbazone, have been synthesized and characterized by elemental analysis, IR, MS, NMR and single-crystal X-ray diffraction studies. Biological studies, carried out in vitro against selected bacteria and the K562 leukemia cell lines, respectively, have shown that the free ligand and its two complexes may be endowed with important biological properties, especially HL with MIC = 3.90 μg/mL against Pseudomonas aeruginosa, the zinc(II) complex 1 with IC50 = 1.0 μM against K562 leukemia cell lines, respectively. The compounds HL and 1 may exert their cytotoxicity activity via induced loss of mitochondria membrane potential (MMP).2-Acetylpyrazine N(4)-phenylthiosemicarbazone (HL) and its metal complexes formulated as [Zn(L)2]2·H2O (1) and [Bi(L)(NO3)2(CH3OH)] (2) have been synthesized and structurally characterized. Biological studies, carried out in vitro against selected bacteria and the K562 leukemia cell lines, respectively, have shown that the free ligand and its complexes may be endowed with important biological properties. Compounds HL and 1 may exert their cytotoxicity via induced loss of MMP.
Co-reporter:Sensen Shang, Junwei Zhao, Lijuan Chen, Yuye Li, Jingli Zhang, Yanzhou Li, Jingyang Niu
Journal of Solid State Chemistry 2012 Volume 196() pp:29-39
Publication Date(Web):December 2012
DOI:10.1016/j.jssc.2012.07.054
Three organic–inorganic hybrid TM–Ln heterometallic phosphotungstates [Cu(dap)2(H2O)][Cu(dap)2]3.5[La(α-HPW11O39)2]·6H2O (1) [Cu(dap)2(H2O)]0.5[Cu(dap)2]4[Nd(α-HPW11O39)2]·4H2O (2) and [Cu(dap)2(H2O)]2[Cu(dap)2]3.5[Eu(α-PW11O39)2]·6H2O (3) (dap=1,2-diaminopropane) have been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectra, optical diffuse reflectance spectra, powder X-ray diffraction (PXRD), thermogravimetric (TG) analyses and single-crystal X-ray diffraction. Their common features are that 1–3 all consist of asymmetric sandwich-type subunits [Ln(α-PW11O39)2]11− and [Cu(dap)2]2+ bridges. Both 1 and 2 display the 2-D (4,4)-topological sheets whereas 3 exhibits the 3-D 5-connected (46·64) topological framework. The magnetic properties of 2 and 3 and the luminescence performance of 3 have been measured.Graphical AbstractThree TM–Ln heterometallic phosphotungstates 1–3 have been synthesized and characterized by elemental analyses, IR spectra, optical diffuse reflectance spectra, X-ray diffraction, thermogravimetric analyses magnetic susceptibility and luminescent properties.Highlights► CuII–LnIII heterometallic polyoxometalates. ► 2-D and 3-D organic–inorganic hybrid phosphotungstates. ► 2-D and 3-D structures consisting of CuII–LnIII heterometals.
Co-reporter:Dongdi Zhang, Chao Zhang, Huanni Chen, Pengtao Ma, Jingping Wang, Jingyang Niu
Inorganica Chimica Acta 2012 Volume 391() pp:218-223
Publication Date(Web):30 August 2012
DOI:10.1016/j.ica.2012.04.030
Three lanthanide (Ln) substituted polyoxometalates [{(α-PW11O39H2)Ln(H2O)(η2,μ-1,1)-CH3COO}2]10− (Ln = Dy(III) for 1, Y(III) for 2, Lu(III) for 3) have been synthesized successfully in moderate aqueous solution and characterized by elemental analyses, IR spectra, UV spectroscopy, thermogravimetric analyses, fluorescence spectra, X-ray powder diffraction (XRPD) and single-crystal X-ray diffraction. The structure analyses reveal that 1–3 are isostructural and constructed by two mono-lanthanide substituted units [(α-PW11O39H2)Ln(H2O)(η2,μ-1,1)-CH3COO]5−, which are bridged by two (η2,μ-1,1)-acetato ligands. The solid-state photoluminescence properties of 1–3 were studied and the results indicate that only 1 demonstrates yellow luminescence. Magnetic measurements reveal that 1 shows spin–orbital coupling interactions and weak antiferromagnetic exchange interactions.Graphical abstractThree isostructural lanthanide (Ln) substituted polyoxometalates [{(α-PW11O39H2)Ln(H2O)(η2,μ-1,1)-CH3COO}2]10− (Ln = Dy(III) for 1, Y(III) for 2, Lu(III) for 3) have been obtained, which are constructed by two mono-lanthanide substituted units [(α-PW11O39H2)Ln(H2O)(η2,μ-1,1)-CH3COO]5− bridged by two (η2,μ-1,1)-acetato ligands.Highlights► Dy, Y and Lu substituted the monovacant polyoxometalates. ► Two mono-lanthanide substituted units construct the dimer. ► Bridged by two (η2,μ-1,1)-acetato ligands. ► Dy demonstrates yellow luminescence. ► Lu shows spin–orbital coupling interactions and weak antiferromagnetic exchange interactions.
Co-reporter:Dongdi Zhang, Suzhi Li, Jingping Wang, Jingyang Niu
Inorganic Chemistry Communications 2012 Volume 17() pp:75-78
Publication Date(Web):March 2012
DOI:10.1016/j.inoche.2011.12.018
Co-reporter:Yanmei Zhou, Hua Zhou, Tongsen Ma, Junli Zhang, Jingyang Niu
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2012 Volume 88() pp:56-59
Publication Date(Web):March 2012
DOI:10.1016/j.saa.2011.11.054
A new Schiff base based on vanillin and naphthalimide was designed and synthesized as fluorescent probe. The probe showed high selectivity for Ag+ over other metal ions such as Pb2+, Na+, K+, Cd2+, Ba2+, Cr3+, Zn2+, Cu2+, Ni2+, Ca2+, Al3+ and Mg2+ in aqueous solution. A new fluorescence emission was observed at 682 nm in the presence of Ag+ ion. The fluorescence intensity quenched with increasing the concentration of Ag+ at 682 nm. The method of job's plot confirmed the 1:2 complex between Ag+ and probe, and the mechanism was proposed.Graphical abstractHighlights► The study lies in the design and synthesis of a new fluorescent probe (4DVN). ► The probe was synthesized based on vanillin and naphthalimide. ► The probe showed high selectivity for Ag+ over other metal ions in aqueous solution. ► The probe was sensitivity to high pH.
Co-reporter:Yanmei Zhou, Hua Zhou, Junli Zhang, Lin Zhang, Jingyang Niu
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2012 Volume 98() pp:14-17
Publication Date(Web):December 2012
DOI:10.1016/j.saa.2012.08.025
A novel and simple Schiff base composed with 9-anthraldehyde and 4-aminoantipyrine was synthesized and characterized as a fluorescent probe. In the presence of Fe3+, the fluorescent intensity has a dramatic enhancement over other examined metal ions in aqueous solution. The method of Job’s plot indicated the formation of 1:1 complex between probe and Fe3+, and the possible binding mode of the system was also proposed. Moreover, other examined metal ions had no effect on the detection of Fe3+.Graphical abstractHighlights► We designed and synthesized a new Schiff base fluorescent probe. ► The probe showed high sensitivity for Fe3+ over other metal ions in aqueous solution. ► The other metal ions have no effect on the detection of Fe3+.
Co-reporter:Chunzhang Wang, Donghui Yang, Jianjuan Wang, Pengtao Ma, Jingping Wang, Jingyang Niu
Journal of Molecular Structure 2012 1011() pp: 1-7
Publication Date(Web):
DOI:10.1016/j.molstruc.2011.04.026
Co-reporter:Juan Zhao, Junwei Zhao, Pengtao Ma, Jingping Wang, Jingyang Niu, Junsheng Wang
Journal of Molecular Structure 2012 1019() pp: 61-67
Publication Date(Web):
DOI:10.1016/j.molstruc.2012.03.038
Co-reporter:Dongdi Zhang, Shaowei Zhang, Pengtao Ma, Jingping Wang, Jingyang Niu
Inorganic Chemistry Communications 2012 20() pp: 191-195
Publication Date(Web):
DOI:10.1016/j.inoche.2012.03.006
Co-reporter:Shaowei Zhang;Dr. Junwei Zhao;Pengtao Ma;Dr. Jingyang Niu; Jingping Wang
Chemistry – An Asian Journal 2012 Volume 7( Issue 5) pp:966-974
Publication Date(Web):
DOI:10.1002/asia.201100918
Abstract
Five rare-earth–transition-metal (RE–TM) heterometal organic–inorganic hybrids based on Keggin-type silicotungstates and mixed ligands H2pzda (pzda=pyrazine-2,3-dicarboxylate) and en (en=ethylenediamine) (enH2)[Cu(en)2(H2O)]2{[Cu(en)2][Cu(en)2(H2O)][(α-SiW11 O39)RE(H2O)(pzda)]}2⋅n H2O (n≈4; RE=YIII (1), DyIII (2), YbIII (3), and LuIII (4)) and [Cu(en)2(H2O)]2{[Cu(en)2]2[Cu(pzda)2][(α-H2SiW11O39)Ce(H2O)]2}⋅n H2O (5; n≈8) have been hydrothermally synthesized and structurally characterized. Compounds 1–5 all contain the dimeric mono-RE substituted Keggin [RE(α-SiW11O39)]210− subunits linked by H2pzda ligands. Interestingly, 1–4 exhibit discrete structures, in which the H2pzda ligand acts as a tetradentate ligand to bind the RE and Cu cations, whereas 5 displays a 1D double-chain architecture, in which the H2pzda ligand adopts a new pentadentate mode to connect the Ce and Cu cations. To our knowledge, 1–5 represent the first monovacant Keggin-type silicotungstates containing both RE–TM heterometals and mixed ligands. The luminescence of 2 is derived from the combination of the DyIII cations and H2pzda ligands, whereas the luminescence properties of 1 and 3–5 are attributable to the H2pzda ligands.
Co-reporter:Yanmei Zhou, Junli Zhang, Hua Zhou, Qingyou Zhang, Tongsen Ma, Jingyang Niu
Sensors and Actuators B: Chemical 2012 s 171–172() pp: 508-514
Publication Date(Web):
DOI:10.1016/j.snb.2012.05.021
Co-reporter:Dongbin Dang, Guangshui Zheng, Yan Bai, Fan Yang, Hui Gao, Pengtao Ma, and Jingyang Niu
Inorganic Chemistry 2011 Volume 50(Issue 17) pp:7907-7909
Publication Date(Web):August 9, 2011
DOI:10.1021/ic200159w
Two polyoxometalate-based silver(I) compounds including a three-dimensional porous crystalline array and a double-helicate bisupporting cluster were achieved using metal–organic helicates and Keggin [PMo12O40]3– as secondary building blocks.
Co-reporter:Jingyang Niu, Guan Wang, Junwei Zhao, Yunxia Sui, Pengtao Ma, and Jingping Wang
Crystal Growth & Design 2011 Volume 11(Issue 4) pp:1253
Publication Date(Web):February 8, 2011
DOI:10.1021/cg1014829
A series of novel organic−inorganic hybrids containing [Nb10O28]6− building blocks [Ni(2,2′-bipy)2]3 [Nb10O28]·2H2O (1), [Ni(2,2′-bipy)3]{[Ni(2,2′-bipy)2]2[Nb10O28]}·8.5H2O (2), [M(phen)3]{[M(phen)2]2[Nb10O28]}·8H2O (M = NiII for 3; M = ZnII for 4; M = CoII for 5) (2,2′-bipy = 2,2′-bipydine, phen = 1,10-phenanthroline) have been successfully synthesized using the hydrothermal method by introducing different transition-metal complexes and fully characterized by elemental analyses, X-ray powder diffraction (XRPD), IR spectroscopy, UV spectroscopy, single-crystal X-ray diffraction analyses, and thermogravimetric analyses. 1 is a one-dimensional (1D) infinite chain polyoxoniobate built by [Nb10O28]6− units and [Ni(2,2′-bipy)2]36+ cations. Furthermore, adjacent chains in 1 are further interacted by π−π stacking interactions resulting in a three-dimensional (3D) supramolecular network. 2−5 are constructed from [Nb10O28]6− units and different transition-metal complexes, in which neighboring units are combined together via the π−π interactions between pyridine rings of ligands forming a 1D linear supramolecular chain. Moreover, the photoluminescence properties of 1 and 3−5 have been investigated. Electron paramagnetic resonance (EPR) spectra reveal that high-spin CoII ions in 5 inhibit the octahedral environments.
Co-reporter:Junwei Zhao, Dongying Shi, Lijuan Chen, Pengtao Ma, Jingping Wang and Jingyang Niu
CrystEngComm 2011 vol. 13(Issue 10) pp:3462-3469
Publication Date(Web):11 Mar 2011
DOI:10.1039/C0CE00983K
Two multi-nickel substituted arsenotungstate aggregates [enH2]2[Ni(H2O)4]2[Ni(en)2]2[Ni(en)]2{[(α-AsW6O26)Ni6(OH)2(H2O)3(en)(B-α-AsW9O34)]2[W4O16][Ni3(H2O)2(en)]2}·16H2O (1) and [Ni(H2O)(en)2]2[Ni(H2O)3(en)][Ni(H2O)(en)]{[(α-AsW6O26)Ni6(OH)2(en)2.5(B-α-AsW9O34)]2H4[W4O16][Ni4(H2O)2(en)2]2}·13H2O (2) (en = ethylenediamine) have been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectra, UV spectra and single-crystal X-ray diffraction. 1 is a 1D chain architecture built by eighteen NiII substituted {[(α-AsW6O26)Ni6(OH)2(H2O)3(en)(B-α-AsW9O34)]2[W4O16][Ni3(H2O)2(en)]2}16− units via two [Ni(H2O)4]2+ and two [Ni(en)2]2+ bridges. 2 also displays a 1D chain motif constructed from twenty NiII substituted {[(α-AsW6O26)Ni6(OH)2(en)2.5(B-α-AsW9O34)]2H4[W4O16][Ni4(H2O)2(en)2]2}8− units via single en bridges. Notably, 1 and 2 not only represent rare eighteen/twenty NiII substituted arsenotungstates, but also display an unusual construction motif simultaneously containing the trivacant Keggin [B-α-AsW9O34]9−, hexavacant Keggin [α-AsW6O26]11− and tetrameric [W4O16]8− fragments. Magnetic measurements demonstrate that 1 and 2 indicate the ferromagnetic couplings within NiII centers.
Co-reporter:Qiuxia Han, Pengtao Ma, Junwei Zhao, Ziliang Wang, Wenhua Yang, Penghu Guo, Jingping Wang, and Jingyang Niu
Crystal Growth & Design 2011 Volume 11(Issue 2) pp:436-444
Publication Date(Web):January 7, 2011
DOI:10.1021/cg101125m
Three novel inorganic−organic hybrid arsenomolybdates constructed from monocapped trivacant [AsIIIAsVMo9O34]6− fragments with [Cu(en)2]2+ or [Cu(dap)2]2+ linkers, [Cu(en)2H2O]2{[Cu(en)2][Cu(en)2AsIIIAsVMo9O34]}2·4H2O (1), (H2en)1.5[Cu(en)(Hen)][AsIIIAsVMo9O34]·2H2O (2) (en = ethylenediamine), and [Cu(dap)2]4[Cu(dap)2(H2O)][Cu(dap)2(AsIIIAsVMo9O34)2]·2H2O (3) (dap = 1,2-diaminopropane), have been successfully synthesized under hydrothermal conditions and structurally characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, and thermogravimetric (TG) analysis. Single-crystal structural analyses indicate that 1−3 all contain the peculiar monocapped trivacant [AsIIIAsVMo9O34]6− subunit derived from the infrequent trivacant Keggin [A-α-AsVMo9O34]9− fragment with a capping {AsO3} group. Notably, 1−3 represent rare inorganic−organic hybrid heteropolymolybdate (HPM) containing [AsIIIAsVMo9O34]6− subunits, which display the assembly from a zero-dimensional sandwich-type dimer, one-dimensional chain, to a two-dimensional layer by the [Cu(en)2]2+ or [Cu(dap)2]2+ linkers. Surface photovoltage spectroscopy (SPS) and electric field induced surface photovoltage spectroscopy (EFISPS) measurements for 1−3 indicate that only 3 has the n-type semiconductor characteristic.
Co-reporter:Lijuan Chen, Dongying Shi, Junwei Zhao, Yulong Wang, Pengtao Ma, Jingping Wang, and Jingyang Niu
Crystal Growth & Design 2011 Volume 11(Issue 5) pp:1913-1923
Publication Date(Web):March 22, 2011
DOI:10.1021/cg200077r
Three novel transition-metal substituted polyoxotungstates based on Keggin fragments, Cs3K3[Co(H2O)6]2[Co(H2O)3(α-GeW11CoO38)3]·30H2O (1), K18{[Mn(H2O)3]2[Mn(H2O)2][(B-β-SiW9O33(OH))Mn3(H2O)(B-β-SiW8O30(OH))]2}·16H2O (2), and K8[Cd(H2O)3]2[Cd4(H2O)2(B-α-SiW9O34)2]·20H2O (3), have been synthesized by reaction of dilacunary Keggin precursors K8[γ-GeW10O36]·6H2O/K8[γ-SiW10O36]·12H2O with transition-metal salts at ambient temperature and characterized by inductively coupled plasma (ICP) analyses, IR spectra, UV spectra, and single-crystal X-ray diffraction. The polyoxoanion of 1 is a novel trimer constructed from three mono-CoII substituted Keggin fragments [α-GeW11CoO38]4− linked by six W−O−Co/W bridges and a capping [Co(H2O)3]2+ bridge. 2 displays the one-dimensional chain built by tetrameric {[Mn(H2O)3]2[Mn(H2O)2][(B-β-SiW9O33(OH))Mn3(H2O)(B-β-SiW8O30(OH))]2}18− units, which is the first one-dimensional silicotungstate containing asymmetric sandwich-type moieties constructed from [B-β-SiW9O34]10− and [B-β-SiW8O31]10− fragments. 3 utilizes the two-dimensional sheet established by tetra-CdII substituted sandwich-type [Cd4(H2O)2(B-α-SiW9O34)2]12− units and [Cd(H2O)3]2+ linkers, representing the first two-dimensional (3,6)-topological network with a Schläfli symbol of 364653 built by sandwich-type Keggin units in polyoxometalate chemistry. Magnetic susceptibility measurements indicate antiferromagnetic exchange interactions within CoII ions in 1 and within MnII ions in 2. The best least-squares fitting values for 2 are J = −1.16 cm−1 and g = 2.13 based on the isostropic spin model. Furthermore, the room-temperature solid-state photoluminescence of 3 displays two emission bands, which are derived from O → Cd ligand-to-metal charge transfer transitions and O → W ligand-to-metal charge transfer transitions, respectively.
Co-reporter:Jingyang Niu, Linping Yang, Junwei Zhao, Pengtao Ma and Jingping Wang
Dalton Transactions 2011 vol. 40(Issue 33) pp:8298-8300
Publication Date(Web):21 Jul 2011
DOI:10.1039/C1DT11042J
Three novel octatungstate-supported tricarbonyl metal derivatives have been synthesized and characterized, which represent the first examples of isopolyoxotungstates-supported carbonyl metal compounds.
Co-reporter:Suzhi Li;Dongdi Zhang;Yuanyuan Guo;Pengtao Ma;Junwei Zhao;Jingping Wang;Jingyang Niu
European Journal of Inorganic Chemistry 2011 Volume 2011( Issue 35) pp:5397-5404
Publication Date(Web):
DOI:10.1002/ejic.201100944
Abstract
Six rare-earth (RE) metal constructed 3D metal–organic frameworks, [RE(pydc)(H2O)n]4[SiW12O40]·4H2O [RE = TmIII (1), YIII (2), PrIII (3), LaIII (4), SmIII (5), EuIII (6); n = 3 (1, 2), 4 (3–6); H2pydc = pyridine-2,6-dicarboxylic acid], have been synthesized and characterized by elemental analyses, inductively coupled plasma techniques, IR and UV spectroscopy, thermogravimetric analyses (for 1 and 3), X-ray powder diffraction, and single-crystal X-ray diffraction. The structural analyses indicate that 1–6 are basically isostructural and show a rare host 3D framework that contains [SiW12O40]4– Keggin polyoxoanions as templates. Photoluminescence measurements reveal that 1–5 show the luminescence of pydc ligands, whereas 6 displays a unique red luminescence.
Co-reporter:Pengtao Ma, Guan Wang, Guo Chen, Jingping Wang, Jingyang Niu
Journal of Molecular Structure 2011 Volume 997(1–3) pp:126-130
Publication Date(Web):28 June 2011
DOI:10.1016/j.molstruc.2011.05.010
A new two-dimensional (2D) polyoxoniobate K2[Cu(H2O)6]{[Nb6O19][Cu(NH3)]2}·8H2O (1) has been synthesized by the diffusion method and structurally characterized by elemental analyses, infrared (IR) spectrum, ultraviolet (UV) spectroscopy, X-ray photoelectron spectroscopy (XPS), thermogravimetric (TG) analysis and single crystal X-ray diffraction. Crystal structure analysis reveals that 1 exhibits a novel 2D network architecture constructed from Lindqvist-type [Nb6O19]8− polyoxoanions and copper coordinated cations. The XPS measurement indicates the oxidation state of Cu ion is +2. Surface photovoltage spectroscopy (SPS) and electric field induced surface photovoltage spectroscopy (EFISPS) measurements indicate that 1 possesses the n-type semiconductor characteristic.Highlights► A new 2D polyoxoniobate has been synthesized by the diffusion method. ► 1 exhibits a novel 2D network architecture constructed from Lindqvist-type polyoxoanions and copper coordinated cations. ► The successful synthesis of 1 enriches the structural diversity of Nb-POMs.
Co-reporter:Ke Wang, Pengtao Ma, Qingxia Yan, Jingping Wang, Jingyang Niu
Inorganic Chemistry Communications 2011 Volume 14(Issue 9) pp:1377-1380
Publication Date(Web):September 2011
DOI:10.1016/j.inoche.2011.05.026
A novel hexasubstituted organosilyl derivative based on trivacant tungstosilicate [(C4H9)4N]3[α-A-SiW9O34(CH3SiOH)6]·3H2O (1), was synthesized under phase-transfer conditions, by the reaction of the CH3SiHCl2 with Na10[α-SiW9O34]∙18H2O, which was characterized by IR spectrum, elemental analyses and X-ray single crystal diffraction. X-ray structural analysis reveals that 1 crystallizes in hexagonal space group R3m, with lattice constants a = 26.0333(2) Å, b = 26.0333(2) Å, c = 13.7239(2) Å, V = 8055.02(15) Å3, and Z = 3, which consists of a trivacant Keggin moiety [α-A-SiW9O34]10−, on which six {CH3Si} groups are grafted via six SiOW bridges, and that each of the six {CH3Si} groups links with two adjacent ones through SiOSi bridges resulting in a unique flower basket-shaped polyoxoanion framework.A novel hexasubstituted organosilyl derivative based on trivacant tungstosilicate [(C4H9)4 N]3H[α-ASiW9O34(CH3SiO)6]·3H2O was synthesized under phase-transfer conditions. The compound displays an open flower basket-shaped framework.Research highlights► A hexasubstituted organosilyl derivative based on trivacant POMs was synthesized. ► The compound has been characterized by IR spectrum, elemental analyses. ► The compound consists of a [α-A-SiW9O34]10− and a cyclic hexameric (CH3SiO)6 group. ► The polyoxoanion represents a novel flower basket-shaped open framework.
Co-reporter:Pengtao Ma, Lijuan Chen, Junwei Zhao, Wei Wang, Jingping Wang, Jingyang Niu
Inorganic Chemistry Communications 2011 Volume 14(Issue 2) pp:415-418
Publication Date(Web):February 2011
DOI:10.1016/j.inoche.2010.12.015
A novel inorganic–organic hybrid 1D chain tungstoarsenate (H2en)4H20{Co(Hen) [Co6As3W24O94(H2O)2]}2·15H2O (en = ethylenediamine) (1) has been hydrothermally synthesized and characterized by elemental analysis, IR spectrum and single-crystal X-ray diffraction. 1 contains a double banana-shaped tungstoarsenate anion {Co(Hen)[Co6As3W24O94(H2O)2]}228−, which is established by two banana-shaped {Co(Hen)[Co6As3W24O94(H2O)2]}14− subunits linked together by a W–O–Co bridge. More importantly, adjacent double banana-shaped polyoxoanions {Co(Hen)[Co6As3W24O94(H2O)2]}228− are interconnected by W–O–Co linkers leading to the 1D chain architecture, to our knowledge, which represents the first inorganic–organic hybrid 1D chain constructed from double banana-shaped polyoxoanions. Magnetic measurements indicate that there are the antiferromagnetic interactions within the cobalt centers.The first inorganic–organic hybrid 1D chain tungstoarsenate (H2en)4H20{Co(Hen)[Co6As3W24O94(H2O)2]}2·15H2O built by double banana-shaped units {Co(Hen)[Co6As3W24O94(H2O)2]}228− has been hydrothermally synthesized and structurally characterized.Research Highlights► A new inorganic–organic hybrid tungstoarsenate contains double banana-shaped anions. ► The hybrid represents the first 1D chain based double banana-shaped polyoxoanions. ► The [Co(Hen)]3+ cation displays an uncommon end-on coordination motif in POM field. ► Antiferromagnetic exchange interactions exist in trinuclear CoII clusters.
Co-reporter:Lijuan Chen, Dongying Shi, Junwei Zhao, Yulong Wang, Pengtao Ma, Jingyang Niu
Inorganic Chemistry Communications 2011 Volume 14(Issue 6) pp:1052-1056
Publication Date(Web):June 2011
DOI:10.1016/j.inoche.2011.03.071
A novel 2-D organic–inorganic hybrid tetra-CoII-substituted sandwich-type Keggin germanotungstate {[Co(dap)2(H2O)]2[Co(dap)2]2[Co4(Hdap)2(B-α-HGeW9O34)2]}·7H2O (1) (dap = 1,2-diaminopropane) has been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectrum, UV spectrum, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. Structural analysis shows that 1 displays a rare 2-D (4,4)-topological network constructed by tetra-CoII-substituted sandwich-type Keggin germanotungstate units and [Co(dap)2]2+ bridges. To our knowledge, 1 represents the first 2-D organic–inorganic hybrid cobalt-substituted sandwich-type polyoxotungstate. Magnetic preperties of 1 have been investigated. The decrease of the product of the molar magnetic susceptibility at higher temperatures results from the spin-orbit coupling of the CoII ion and/or the antiferromagnetic interactions whereas the maximum at the lower temperatures is indicative of the ferromagnetic interactions within the tetranuclear CoII spin cluster in the sandwich belt.A novel 2-D organic–inorganic hybrid tetra-CoII-substituted sandwich-type Keggin germanotungstate has been hydrothermally synthesized and structurally characterized. Its magnetic preperties have been investigated.Research highlights► Sandwich-type Keggin germanotungstate. ► 2-D organic–inorganic hybrid tetra-CoII-substituted sandwich-type polyoxometalate. ► 2-D (4,4)-topological network consisting of sandwich-type units. ► The ferromagnetic interactions within the CoII spin cluster. ► The spin-orbit coupling of the CoII ion.
Co-reporter:Qiuxia Han, Pengtao Ma, Junwei Zhao, Jingping Wang, Jingyang Niu
Inorganic Chemistry Communications 2011 Volume 14(Issue 5) pp:767-770
Publication Date(Web):May 2011
DOI:10.1016/j.inoche.2011.03.008
A novel transition metal substituted tungstoarsenate [Cu2(phen)2(μ-ox)]{[Cu(phen)(H2O)2][Cu4 (H2O)4Cu2(phen)2(AsW9O33)2]}·6H2O (ox = oxalate, phen = 1,10-phenanthroline) (1) has been synthesized by reaction of K14[As2W19O67(H2O)]·nH2O, CuCl2·2H2O, H2C2O4·2H2O and phen under hydrothermal conditions and characterized by elemental analyses, IR and UV spectra and X-ray single-crystal diffraction. 1 displays a 1D chain architecture constructed by alternating hexa-Cu sandwiched units {[Cu(phen)(H2O)2]2[Cu4(H2O)4Cu2(phen)2(AsW9O33)2]}2− and dinuclear copper(II)-oxalate complexes [Cu2(phen)2(μ-ox)]2+. The 3D supramolecular network can be established by intra- and inter-molecular π–π packing interactions. To the best of our knowledge, 1 represents the first 1D chain-like inorganic–organic hybrid tungstoarsenate with mixed organic ligands containing hexa-nuclear sandwiched units bridged by copper-oxalate complex linkers.The first example of 1D chain-like inorganic–organic hybrid tungstoarsenate with mixed organic ligands containing hexa-nuclear sandwiched units bridged by copper-oxalate complex linkers has been prepared.Research Highlights► A novel TMC-substituted tungstoarsenate displays 1D chain architecture. ► Hexa-Cu sandwich-type polyanions and di-Cu complexe cations alternating connected. ► The first 1D chain-like hybrid tungstoarsenate with mixed organic ligands. ► π–π interactions between the neighboring phen ligands leading to the 3D framework.
Co-reporter:Yun Liu, Dongying Shi, Junwei Zhao, Lijuan Chen, Zhiqiao Wang, Pengtao Ma, Jingyang Niu
Inorganic Chemistry Communications 2011 Volume 14(Issue 7) pp:1178-1182
Publication Date(Web):July 2011
DOI:10.1016/j.inoche.2011.04.021
A novel organic–inorganic hybrid dimeric arsenotungstate [enH2]4{[Cu(en)2][(A-β-H2AsW9O34)Cu(en)2]2}·8H2O (1) has been prepared by reaction of Na8[A-α-HAsW9O34]·11H2O with CuCl2·2H2O and ErCl3 in the presence of ethylenediamine (en) under hydrothermal conditions and structurally characterized by elemental analyses, IR spectra, UV spectra, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. The skeleton of 1 exhibits an interesting centric dimeric structure formed by two opposite trivacant Keggin [(A-β-H2AsW9O34)Cu(en)2]5− subunits linked by a [Cu(en)2]2+ connector, which represents a rare organic–inorganic hybrid arsenotungstate consisting of [A-β-AsW9O34]9− fragments. Interestingly, the trivacant Keggin precursor [A-α-AsW9O34]9− has been isomerized to the trivacant Keggin fragment [A-β-AsW9O34]9− in 1 under hydrothermal conditions. The photocatalytic measurement illustrates that 1 can effectively inhibit the photodegradation of rhodamine-B.A novel organic–inorganic hybrid dimeric arsenotungstate [enH2]4{[Cu(en)2][(A-β-H2AsW9O34)Cu(en)2]2}·8H2O has been prepared, which can effectively inhibit the photodegradation of rhodamine-B.Research highlights► Organic–inorganic hybrid dimeric arsenotungstate. ► The hybrid arsenotungstate consisting of [A-β-AsW9O34]9− fragments. ► The hydrothermal isomerization of [A-α-AsW9O34]9− to [A-β-AsW9O34]9−.► The photodegradation of rhodamine-B.
Co-reporter:Dongying Shi, Lijuan Chen, Junwei Zhao, Yu Wang, Pengtao Ma, Jingyang Niu
Inorganic Chemistry Communications 2011 Volume 14(Issue 1) pp:324-329
Publication Date(Web):January 2011
DOI:10.1016/j.inoche.2010.11.028
The reaction of 2(NH4)2SO4Ce(SO4)2·2H2O or DyCl3 with CuCl2·2H2O, Na9[A-α-PW9O34]·7H2O in the presence of ethylenediamine (en) or 1,2-diaminopropane (dap) under hydrothermal conditions led to two novel 2D organic–inorganic hybrid monovacant Keggin phosphotungstate 3d–4f heterometallic derivatives [Cu(en)2]2H6 [Ce(α-PW11O39)2]·8H2O (1) and [Cu(dap)2(H2O)][Cu(dap)2]4.5[Dy(α-PW11O39)2]·4H2O (2), which were structurally characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. 1 displays an interesting 2D 3d–4f heterometallic sheet architecture with a 4-connected topology constructed from 1:2-type [Ce(α-PW11O39)2]10– subunits and [Cu(en)2]2+ bridges whereas 2 illustrates the other unique 2D 3d–4f heterometallic sheet with a 5-connected topology established by 1:2-type [Dy(α-PW11O39)2]11− subunits and [Cu(dap)2]2+ bridges. To the best of our knowledge, 1 and 2 represent scare organic–inorganic hybrid 2D 3d–4f heterometallic monovacant Keggin phosphotungstates. Moreover, the solid-state photoluminescence of 2 was investigated.Two novel 2D monovacant Keggin phosphotungstate 3d–4f heterometallic derivatives [Cu(en)2]2H6 [Ce(α-PW11O39)2]·8H2O (1) and [Cu(dap)2(H2O)][Cu(dap)2]4.5[Dy(α-PW11O39)2]·4H2O (2) have been hydrothermally synthesized and structurally characterized.Research Highlights► 2D organic-inorganic hybrid 3d-4f heterometallic Keggin phosphotungstates. ► 2D 4-connected topological 3d-4f Keggin phosphotungstate. ► 2D 5-connected topological 3d-4f Keggin phosphotungstate. ► photoluminescent 3d-4f heterometallic polyoxometalate. ► This finding will spur the exploration on 3d-4f heterometallic polyoxometalates.
Co-reporter:Yuanyuan Guo, Pengtao Ma, Jingping Wang, Jingyang Niu
Journal of Solid State Chemistry 2011 Volume 184(Issue 11) pp:3121-3127
Publication Date(Web):November 2011
DOI:10.1016/j.jssc.2011.09.030
Two novel zinc coordination polymers [Zn2(H2O)L(MoO4)]n (1) and [Zn4(PO4)2L′(H2O)]n (2) (H2L=2,2′-bipyridine-6.6′-dicarboxylic acid, H2L′=2,2′-bipyridine-4,4′-dicarboxylic acid) have been hydrothermally synthesized and characterized by elemental analyses, IR spectra, UV spectra, single-crystal X-ray diffraction and thermogravimetric analyses. Structural analyses indicate that 1 represents a 2-D sheet structure built by dimeric [Zn2L(H2O)]2+ units and MoO42– groups whereas 2 displays an interesting 3-D framework constructed by tetranuclear zinc clusters, L′2− ligands and PO43– groups. Examination of UV spectra suggests that both 1 and 2 can stably exist in the pH range of 2.45–5.45 and 3.01–8.55 in aqueous solution, respectively. The room-temperature solid-state photoluminescence of 1 and 2 are derived from the intra-ligands π–π⁎ transitions of H2L and H2L′ ligands and the ligand-to-metal-charge-transfer transitions.Graphical AbstractTwo new transition metal coordination polymers, namely, [Zn2(H2O)L1(MoO4)]n (1), [Zn4(PO4)2L2(H2O)]n (2) (H2L1=2,2′-bipyridine-6,6′-dicarboxylic acid, H2L2=2,2′-bipyridine-4,4′-dicarboxylic acid) have been hydrothermally synthesized. 1 represents a 2-D sheet structure while 2 represents 3-D network.Highlights►Two new transition metal coordination polymers have been hydrothermally synthesized. ► The two compounds have been characterized by elemental analyses, IR, UV spectra, single-crystal X-ray diffraction, thermogravimetric analyses and photoluminescence. ► Compound 1 represents a 2-D sheet structure while 2 represents 3-D network.
Co-reporter:Junwei Zhao, Qiuxia Han, Dongying Shi, Lijuan Chen, Pengtao Ma, Jingping Wang, Jingyang Niu
Journal of Solid State Chemistry 2011 Volume 184(Issue 10) pp:2756-2761
Publication Date(Web):October 2011
DOI:10.1016/j.jssc.2011.08.016
A S-shaped multi-iron substituted arsenotungstate [enH2]2[(α-H2AsVW6O26)Fe3(H2O)(B-α-H4AsVW9O34)]2[Fe]2·8H2O (1) (en=ethylenediamine) has been prepared by reaction of K14[As2IIIW19O67(H2O)]·nH2O with Fe2(SO4)3·xH2O under hydrothermal conditions and structurally characterized by elemental analyses, IR spectra, UV spectra, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. The skeleton of 1 consists of two asymmetric sandwich-type subunits [(α-H2AsVW6O26)Fe3(H2O)(B-α-H4AsVW9O34)]5− linked by a di-FeIII cluster. Moreover, magnetic susceptibility measurements demonstrate that 1 indicates the antiferromagnetic coupling interactions within FeIII centers with the best-fitting set of parameters of J1=−7.07 cm−1, J2=−0.45 cm−1 and g=2.05, which are generated by the addition of the expressions of the molar susceptibilities of two tri-FeIII clusters and one di-FeIII cluster derived from for spin pairs coupled through the isotropic exchange interactions.Graphical abstractS-shaped multi-iron substituted arsenotungstate consisting of two asymmetric sandwich-type subunits has been hydrothermally synthesized and structurally characterized. Its magnetic properties have been investigated.Highlights► Multi-iron substituted arsenotungstate. ► Symmetric sandwich-type subunits. ► Antiferromagnetic coupling interactions within FeIII centers. ► Hexavacant Keggin POM fragments.
Co-reporter:Ming-Xue Li, Dong Zhang, Li-Zhi Zhang, Jing-Yang Niu, Bian-Sheng Ji
Journal of Organometallic Chemistry 2011 696(4) pp: 852-858
Publication Date(Web):
DOI:10.1016/j.jorganchem.2010.10.011
Co-reporter:Suzhi Li, Pengtao Ma, Jingping Wang, Yuanyuan Guo, Haizhu Niu, Junwei Zhao and Jingyang Niu
CrystEngComm 2010 vol. 12(Issue 6) pp:1718-1721
Publication Date(Web):19 Feb 2010
DOI:10.1039/B924394A
A rare three-dimensional organic–inorganic compound based on the Anderson-type polyoxometalate anion, [Na4(H2O)14Cu(PDA)2]H[Al(OH)6Mo6O18]·5H2O (H2PDA = pyrazine-2,3-dicarboxylic acid) (1) has been synthesized, in which each Anderson polyoxoanion [Al(OH)6Mo6O18]3− acts as a decadentate ligand, connecting four tetrameric [Na4(H2O)14]4+ clusters and two [Cu(PDA)2]2− coordination ions through terminal oxygen atoms.
Co-reporter:Ming Xue Li, Chun Ling Chen, Dong Zhang, Jing Yang Niu, Bian Sheng Ji
European Journal of Medicinal Chemistry 2010 Volume 45(Issue 7) pp:3169-3177
Publication Date(Web):July 2010
DOI:10.1016/j.ejmech.2010.04.009
Transition metal complexes Mn(L1)2 (1), Mn(L2)2 (2), Co(L3)2Cl 4H2O (3), Zn(L3)2 DMF (4), Co(HL4)2(ClO4)2 3H2O (5) and Zn(L5)2 DMF (6) where HL1 = 2-acetylpyridine thiosemicarbazone, HL2 = 2-acetylpyridine N(4)-methylthiosemicarbazone, HL3 = 2-benzoylpyridine thiosemicarbazone, HL4 = 2-benzoylpyridine N(4)-methylthiosemicarbazone and HL5 = 2-benzoylpyridine N(4)-phenylthiosemicarbazone, have been synthesized. The complexes 1, 2, 5 and 6 were characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction studies. Preliminary in vitro screening indicated that all the tested compounds showed significant antitumor activity against K562 leucocythemia cancer cell line.Preliminary in vitro screening indicated that all the tested compounds showed significant antitumor activity against K562 leucocythemia cell line.
Co-reporter:Jingyang Niu, Guo Chen, Junwei Zhao, Chunfa Yu, Pengtao Ma, and Jingping Wang
Crystal Growth & Design 2010 Volume 10(Issue 11) pp:4689-4692
Publication Date(Web):September 28, 2010
DOI:10.1021/cg100864m
A novel organic−inorganic hybrid phosphovanado-molybdate Na(H2O)6[Cu(2,2′-bipy)3]2[Cu(1,2-dap)2(H2O)]6H[Cu(1,2-dap)2{PMoVI8VIV4O40(VIVO)2Cu(1,2-dap)2}]6·2H2O (1) (1,2-dap = 1,2-diaminopropane, 2,2′-bipy = 2,2′-bipyridine) has been hydrothermally synthesized and characterized by elemental analyses, IR, TG-DTA, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRPD), and single crystal X-ray diffraction. Interestingly, 1 represents the first example of cyclohexane-like ring-shaped phosphovanadomolybdate constructed from six bicapped pseudo-Keggin clusters [PMoVI8VIV4O40(VIVO)2Cu(1,2-dap)2]5− linked by six [Cu(1,2-dap)2]2+ linkers. Notably, adjacent rings are connected together, forming the 3-D supramolecular structure through hydrogen bonding interactions.
Co-reporter:Ming-Xue Li, Dong Zhang, Li-Zhi Zhang, Jing-Yang Niu, Bian-Sheng Ji
Inorganic Chemistry Communications 2010 Volume 13(Issue 12) pp:1572-1575
Publication Date(Web):December 2010
DOI:10.1016/j.inoche.2010.08.032
2-Acetylpyridine N(4)-cyclohexylthiosemicarbazone (HL) and its manganese(II) and nickel(II) complexes formulated as [Mn(L)2] (1) and [Ni(L)2] (2) have been synthesized and characterized by elemental analysis, infrared spectra, mass spectra, and single-crystal X-ray diffraction studies. In the two complexes, the coordination polyhedron approaches an octahedron, where the two ligands coordinate to the metal via the pyridine nitrogen atom and the nitrogen and sulfur donors of the thiosemicarbazide moiety. Biological studies, carried out in vitro against selected bacteria and K562 leukaemia cell line, respectively, have shown that the free ligand and its complexes exhibited distinct differences in the biological activities.2-Acetylpyridine N(4)-cyclohexylthiosemicarbazone and its manganese(II) and nickel(II) complexes have been synthesized and fully characterized. Biological studies, carried out in vitro against selected bacteria and K562 leukaemia cell line, respectively, have shown that the free ligand and its complexes exhibited distinct differences in the biological activities.Research Highlights► In summary, 2-acetylpyridine N(4)-cyclohexylthiosemicarbazone and its manganese(II) and nickel(II) complexes were synthesized and fully characterized. ► Biological studies showed that the title three compounds all exhibited important antibacterial activities and the coupling of 2-acetylpyridine N(4)-cyclohexylthiosemicarbazone to Mn(II) and Ni(II), respectively, leads to remarkable enhancement of its antitumor activity. ► This confirms the conclusion that the complexation with metals has a synergetic effect on the biological activity of thiosemicarbazones.
Co-reporter:Peng-Tao Ma, Jun-Wei Zhao, Jing-Ping Wang, Yue Shen, Jing-Yang Niu
Journal of Solid State Chemistry 2010 Volume 183(Issue 1) pp:150-156
Publication Date(Web):January 2010
DOI:10.1016/j.jssc.2009.11.001
Three new sandwich-type polyoxotungstates (POTs) decorated by nickel-2,2′-bpy complexes [{Ni(2,2′-bpy)2(H2O)}2{Ni(2,2′-bpy)}2 {Ni4(H2O)2(B-α-XW9O34)2}]n− (X=PV, n=4 for 1; X=AsV, n=4 for 2; X=GeIV, n=4 for 3) (2,2′-bpy=2,2′-bipyridine) were successfully synthesized under hydrothermal conditions and structurally characterized by elemental analyses, IR spectroscopy, single-crystal X-ray diffraction, and magnetic properties. Single-crystal structural analyses indicate that 1 and 2 are isostructural and both crystallize in the monoclinic space group C2/c, whereas 3 belongs to the triclinic space group P1¯. To our knowledge, 1, 2 and 3 represent rare examples of the organic–inorganic hybrid sandwich-type polyoxometalates functionalized by multiple nickel-aromatic amine complexes. Magnetic measurements of 1 exhibit the presence of ferromagnetic interactions within the rhombic tetranuclear-NiII cluster.Three new sandwich-type polyoxotungstates (POTs) decorated by nickel-2,2'-bpy complexes were successfully synthesized under hydrothermal conditions and structurally characterized.
Co-reporter:Lijuan Chen, Junwei Zhao, Pengtao Ma, Qiuxia Han, Jingping Wang, Jingyang Niu
Inorganic Chemistry Communications 2010 Volume 13(Issue 1) pp:50-53
Publication Date(Web):January 2010
DOI:10.1016/j.inoche.2009.10.012
A new organic–inorganic hybrid nickel-substituted arsenotungstate [Na(H2O)3]2[Ni(H2O)6]2[Ni(H2O)5]{[Ni3(dap)(H2O)2]2(H2W4O16)}{(α-H2AsW6O26)[Ni6(OH)2(H2O)(dap)2](B-α-HAsW9O34)}2·7H2O (1) (dap = 1,2-diaminopropane) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal data for 1: C18H144As4N12Na2Ni21O176W34, Mr = 11174.92, triclinic, space group P-1, a = 15.004(4) Å, b = 16.357(5) Å, c = 22.070(6) Å, α = 80.458(5)°, β = 79.291(5)°, γ = 72.074(5)°, V = 5030(3) Å3, Z = 1, GOOF = 1.007, R1 = 0.0703, wR2 = 0.1670. The skeleton of 1 is a centric nanoscale cluster and is composed of two asymmetric sandwich-type clusters {(α-H2AsW6O26)[Ni6(OH)2(H2O)(dap)2](B-α-AsW9O34)}7− linked by a symmetric cluster {[Ni3(dap)(H2O)2]2(H2W4O16)}6+. Notably, 1 is an interesting polyoxometalate containing the trivacant Keggin [B-α-AsW9O34]9−, hexavacant Keggin [α-AsW6O26]11− and tetrameric [W4O16]8− units. Magnetic measurements indicate that 1 shows the ferromagnetic interactions within NiII centers.A new organic–inorganic hybrid nickel-substituted arsenotungstate [Na(H2O)3]2[Ni(H2O)6]2[Ni(H2O)5]{[Ni3(dap)(H2O)2]2(H2W4O16)}{(α-H2AsW6O26)[Ni6(OH)2(H2O)(dap)2](B-α-HAsW9O34)}2·7H2O has been hydrothermally synthesized and structurally characterized, which is the interesting polyoxometalate simultaneously containing the trivacant Keggin [B-α-AsW9O34]9−, hexavacant Keggin [α-AsW6O26]11− and tetrameric [W4O16]8− units.
Co-reporter:Ming-Xue Li, Dong Zhang, Li-Zhi Zhang, Jing-Yang Niu
Inorganic Chemistry Communications 2010 Volume 13(Issue 11) pp:1268-1271
Publication Date(Web):November 2010
DOI:10.1016/j.inoche.2010.07.012
2-Thiophene N(4)-methylthiosemicarbazone (HL) and its Ag(I) complex of formula [Ag6(L)6⋅ 4DMF] 1 have been synthesized and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction studies. The silver(I) complex 1 with a 1:1 metal–ligand molar ratio is an unusual hexanuclear cluster with 6 silver atoms in different environments: four silver atoms of them are considered to be 3-coordinate form, which are coordinated by two thiolate sulfur atoms and one imine nitrogen and the other two silver atoms are considered to be 4-coordinate form, which are coordinated by three thiolate sulfur atoms and one imine nitrogen, with four thiolate sulfur bridging two silver atoms and two thiolate sulfur bridging three silver atoms. Biological studies, carried out in vitro against bacteria, fungi and SMMC-7721 liver cancer cell line, respectively, have shown that the free ligand and the title complex show distinct difference in the biological property.2-Thiophone N(4)-methylthiosemicarbazone and its Ag(I) complex of formula [Ag6(L)6⋅ 4DMF] 1 were synthesized and fully characterized. The silver complex 1 is an unusual hexanuclear cluster with 6 silver atoms in different environments. Biological studies have shown that the free ligand and the title complex show distinct difference in the biological property.
Co-reporter:Suzhi Li, Pengtao Ma, Haizhu Niu, Junwei Zhao, Jingyang Niu
Inorganic Chemistry Communications 2010 Volume 13(Issue 7) pp:805-808
Publication Date(Web):July 2010
DOI:10.1016/j.inoche.2010.03.028
Co-reporter:Junwei Zhao, Dongying Shi, Hongli Cheng, Lijuan Chen, Pengtao Ma, Jingyang Niu
Inorganic Chemistry Communications 2010 Volume 13(Issue 7) pp:822-827
Publication Date(Web):July 2010
DOI:10.1016/j.inoche.2010.04.002
Two novel 1-D copper complexes {[CuII2(Hbpdc)2]Cl2}2·2H2O (1) and CuI(H2bpdc)Cl (2) (H2bpdc = 2,2′- bipyridyl-5,5′-dicarboxylic acid) have been one-pot hydrothermally synthesized by reaction of H2bpdc, CuCl2·2H2O, PrCl3 and glacial acetic acid and structurally characterized by IR spectroscopy, X-ray photoelectron spectroscopy and single-crystal X-ray diffraction. Single-crystal structural analyses show that 1 is a novel 1-D stair-like chain constructed from centric tetra-copper clusters {[CuII2(Hbpdc)2]Cl2}2 by means of Cu–O weak coordination interactions whereas 2 displays a 1-D comb-like chain built by [CuI(H2bpdc)Cl] units through Cl− bridges. More interestingly, 1 and 2 were one-pot hydrothermally synthesized, which is very rare in synthetic chemistry. The photofluorescence properties of 1 and 2 have been investigated.
Co-reporter:Guo Chen;Chunzhang Wang;Pengtao Ma;Jingping Wang
Journal of Cluster Science 2010 Volume 21( Issue 2) pp:121-131
Publication Date(Web):2010 June
DOI:10.1007/s10876-010-0296-8
A novel organic–inorganic hybrid polyoxoniobate K8Na2{[Cu(en)(H2O)]2 [HNb6O19]2}·25H2O (en = ethylenediamine) 1 has been synthesized by the diffusion method and structurally characterized by elemental analyses, IR, UV-Vis spectra, thermogravimetric (TG) analysis and single crystal X-ray diffraction. The structure analysis indicates that 1 consists of two {[Cu(en)(H2O)][HNb6O19]}5− polyoxoanions linked each other by two methane-like {K4Na}5+ cationic clusters. Surface photovoltage spectroscopy (SPS) and electric field induced surface photovoltage spectroscopy (EFISPS) measurements indicate that 1 is the n-type conduction characteristic. In situ UV and CV studies indicate that 1 can stably exist in the larger pH ranges in aqueous solution.
Co-reporter:Jing-Yang Niu Dr.;Guo Chen;Jun-Wei Zhao Dr.;Peng-Tao Ma;Su-Zhi Li Dr.;Jing-Ping Wang ;Ming-Xue Li Dr.;Yan Bai Dr.;Bian-Sheng Ji
Chemistry - A European Journal 2010 Volume 16( Issue 24) pp:7082-7086
Publication Date(Web):
DOI:10.1002/chem.201000824
Co-reporter:X. Fu;P. T. Ma;J. S. Wang;J. Y. Niu
Russian Journal of Coordination Chemistry 2010 Volume 36( Issue 8) pp:622-626
Publication Date(Web):2010 August
DOI:10.1134/S1070328410080129
A new coordination polymer constructed from Dawson-type polyoxotungstate and transition metal complexes [Cu(H2Biim)2]2H2P2W18O2 · 2C2H5OH · 2H2O (H2Biim = 2,2′-diimidazole) (I) have been prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, and TG analysis. The crystal structure of I contains a Dawson-type [α-P2W18O62]6− polyanion, two metal coordination cations [Cu(H2Biim)2]2+, two protons, two ethanol molecules, and two lattice water molecules. Interestingly, a three-dimensional supramolecular framework is formed via N-H⋯O hydrogen bonds. Complex I crystallizes in the monoclinic system, space group C2/c with a = 22.742(3), b = 14.780(2), c = 29.637(5) Å, β = 111.199(2)°, V = 9288(2) Å3, T = 296(2) K, Z = 4, μ = 22.774 mm−1, GOOF = 1.017, R1 = 0.0590 and wR2 = 0.1394.
Co-reporter:G. Chen;H. Y. Niu;W. Wang;J. P. Wang
Russian Journal of Coordination Chemistry 2010 Volume 36( Issue 8) pp:605-609
Publication Date(Web):2010 August
DOI:10.1134/S1070328410080087
A new Keggin-type silicotungstate anion-supported organic-inorganic hybrid transition metal complex, [Zn(Bipy)3]1.5[SiW12O40Zn(Bipy)2(OH)] · 0.25H2O (I) (Bipy = 2,2′-bipyridine), has been synthesized by the hydrothermal method and characterized by elemental analysis, IR, UV, and EPR spectra, TG-DTA analysis, and single crystal X-ray diffraction. The structural analysis indicates that each structural unit of I consists of one [SiW12O40Zn(Bipy)2(OH)]3− heteropolyanion, one and a half isolated [Zn(Bipy)3]2+ cations, and a quarter of crystal water molecule. The [Zn(Bipy)2(OH)]+ unit is covalently bonded to one Keggin polyoxoanion [SiW12O40]4− in the [SiW12O40Zn(Bipy)2(OH)]3− cluster. The EPR spectrum indicates the existence of Zn2+ with the high-spin state, and TG-DTA analysis exhibits that I has two steps of weight loss and the polyoxoanion framework is collapsed at 618°C.
Co-reporter:Jingping Wang, Junwei Zhao, Pengtao Ma, Junchuang Ma, Linping Yang, Yan Bai, Mingxue Li and Jingyang Niu
Chemical Communications 2009 (Issue 17) pp:2362-2364
Publication Date(Web):27 Mar 2009
DOI:10.1039/B822368H
A novel type of heteropolyoxoanion (HPOA) precursors {[Ca (H2O)]6[P4M6O34]2}12− [M = WVI (1), MoVI (2)] has been synthesized and structurally characterized, which represents the rare membership of the HPOA family constituted by two early-transition-metal clusters ([P4M6O34]12−) and a main-group metal cluster of high nuclearity ([Ca6]12+).
Co-reporter:Suzhi Li, Junwei Zhao, Pengtao Ma, Juan Du, Jingyang Niu and Jingping Wang
Inorganic Chemistry 2009 Volume 48(Issue 20) pp:9819-9830
Publication Date(Web):September 21, 2009
DOI:10.1021/ic901330y
Two types of rare sandwich-type germanomolybdates [Na12(H2O)36][Cu2(β-Y-GeMo9O33)2]·3H2O (1), [N(CH3)4]4 [Na6(H2O)24][Cr2(β-Y-GeMo9O33)2]·7H2O (2), and [Na11(H2O)25]H[M4(H2O)2(α-B-GeMo9O34)2]·6H2O (M = NiII for 3, M = MnII for 4 and M = CoII for 5) have been synthesized and characterized by elemental analyses, ICP spectra, IR spectroscopy, UV spectroscopy, thermogravimetry (TG) analyses (for 1−3), X-ray photoelectron spectroscopy (XPS) (for 1 and 3), X-ray powder diffraction (XRPD) (for 1 and 3) and single-crystal X-ray diffraction. To our knowledge, 1−5 represent the first sandwich-type germanomolybdates containing both {β-Y-GeMo9O33}/{α-B-GeMo9O34} fragments and transition-metal clusters. Interestingly, 1 and 2 display the rare dinuclear transition-metal substituted sandwich-type structures with unusual trivacant {β-Y-GeMo9O33} germanomolybdate units whereas 3−5 exhibit the first tetranuclear transition-metal substituted sandwich-type structures with familiar trivacant {α-B-GeMo9O34} germanomolybdate units. Surface photovoltage spectroscopy (SPS) and electric field induced surface photovoltage spectroscopy (EFISPS) measurements reveal that 1 and 3 bear the behavior of the n-type semiconductor. Magnetic measurements indicate 1 and 3 demonstrate antiferromagnetic exchange interactions and ferromagnetic exchange interactions, respectively.
Co-reporter:Junwei Zhao, Qiuxia Han, Pengtao Ma, Lijuan Chen, Jingping Wang, Jingyang Niu
Inorganic Chemistry Communications 2009 Volume 12(Issue 8) pp:707-710
Publication Date(Web):August 2009
DOI:10.1016/j.inoche.2009.05.023
A 65·8 CdSO4-like 3-D framework [Cu(en)2]3[α-AsW11NaO39]·2H2O (1) constructed by monosodium-substituted Keggin arsenotungstates and copper(II)-ethylenediamine complexes (en = ethylenediamine) has been synthesized by reaction of Na8[α-HAsW9O34]·11H2O, CuCl2·2H2O and ethylenediamine under hydrothermal conditions and structurally characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction. Crystal data for 1: C12H52AsCu3N12NaO41W11, monoclinic, Cc, a = 20.409(9) Å, b = 16.737(8) Å, c = 16.561(7) Å, β = 104.607(7)°, V = 5474(4) Å3, T = 296(2) K; Z = 4, μ = 24.860 mm−1, GOOF = 1.086, R1 = 0.0284, wR2 = 0.0759. To the best of our knowledge, 1 represents the first 65·8 CdSO4-like 3-D monovacant Keggin arsenotungstate derivative in polyoxometalate chemistry.A 65·8 CdSO4-like 3-D framework [Cu(en)2]3[α-AsW11NaO39]·2H2O constructed by monosodium-substituted Keggin arsenotungstates and copper(II)-ethylenediamine complexes has been synthesized, representing the first 65·8 CdSO4-like 3-D monovacant Keggin POM derivative in POM chemistry.
Co-reporter:Junwei Zhao, Jili Li, Pengtao Ma, Jingping Wang, Jingyang Niu
Inorganic Chemistry Communications 2009 Volume 12(Issue 6) pp:450-453
Publication Date(Web):June 2009
DOI:10.1016/j.inoche.2009.03.011
An unprecedented 2-D organic–inorganic hybrid sandwich-type polyoxotungstate containing O-donor organic ligands [DMAH]4{[Mn(DMF)4]2[Mn4(DMF)2(α-B-HPW9O34)2]} (1) (DMA = dimethylamine, DMF = N,N-dimethylformamide) has been solvothermally synthesized and characterized by IR, UV spectra and X-ray single-crystal diffraction. The 2-D organic–inorganic hybrid network of 1 is built by tetra-MnII substituted sandwich-type polyoxotungstates [Mn4(DMF)2(α-B-HPW9O34)2]8− and [Mn(DMF)4]2+ cation bridges, which displays the common 2-D (4,4) topological net. It should be noted that the major difference between [Mn4(DMF)2(α-B-HPW9O34)2]8− in 1 and the reported [Mn4(H2O)2(α-B-PW9O34)2]10− is that two DMF ligands substitute two H2O ligands on the Mn4O16 unit located in the sandwich belt. Magnetic susceptibility measurement indicates the occurrence of antiferromagnetic coupling interaction within MnII ions.An unprecedented 2-D organic–inorganic hybrid sandwich-type polyoxotungstate containing O-donor organic ligands [DMAH]4{[Mn(DMF)4]2[Mn4(DMF)2(α-B-HPW9O34)2]} (1) has been solvothermally synthesized and characterized by elemental analysis, IR, UV spectra and X-ray single-crystal diffraction.
Co-reporter:Qinglan ZHAO, Ruijuan HAN, Jili LI, Xiaodi DU, Jingping WANG
Journal of Rare Earths 2009 Volume 27(Issue 2) pp:177-181
Publication Date(Web):April 2009
DOI:10.1016/S1002-0721(08)60215-X
A 1D zigzag polyoxometalate [(CH3)4N]1.50H3.50[Gd(GeW11O39)(H2O)2]·2.5H2O (1) was synthesized by reaction of the monovacant polyanion [α-GeW11O39]8– with Gd3+ ions in aqueous solution and characterized by IR, UV spectra, ICP, and X-ray crystallography. X-ray single-crystal structural analysis indicated that the title compound crystallized in a monoclinic lattice, C2/c space group with a= 2.8201(5), b=2.2885(3), c=2.4033(4) nm, β=123.875 (2)°, V=12.878(4) nm3, Z=8, R1=0.0623, wR2=0.1287. The solid-state structure of the title compound displayed an infinite one-dimensional arrangement built up of [α-GeW11O39]8– polyanions connected by GdIII cations.
Co-reporter:Peng-Tao Ma, Dong-Qin Bi, Jing-Ping Wang, Wei Wang, Jing-Yang Niu
Inorganic Chemistry Communications 2009 Volume 12(Issue 12) pp:1182-1184
Publication Date(Web):December 2009
DOI:10.1016/j.inoche.2009.09.013
In this paper, we reported a novel polyoxotungstate, H6[Ni3W4P4O28]·en·4H2O, which is the first 3-D racemic network that incorporates helical WO6-octahedral chains of different handedness as building blocks. The helices are held together by helically distributed phosphorus and nickel atoms, this steric orientation leads to the generation of a small square hole with the dimensions of 0.85 × 0.85 Å and an irregular pentagonal porous channel with the dimensions of 4.08 × 5.26 Å, in which some water and ethylenediamine molecules filled.The first polyoxotungstate with helical WO6-octahedral chains of different handedness as building blocks is reported, and the helices are held together by helically distributed phosphorus and nickel atoms to form a racemic network.
Co-reporter:J. W. Zhao;X. F. Zhang;P. T. Ma;Y. Q. Feng
Russian Journal of Coordination Chemistry 2009 Volume 35( Issue 12) pp:
Publication Date(Web):2009 December
DOI:10.1134/S1070328409120057
A Keggin organic-inorganic hybrid polyoxometalate combined with nickel complex [Ni (Dmf)3(H2O)][HPMo12O40] · (Dmf) · 2H2O (I) has been synthesized and structurally characterized by elemental analysis, IR spectrum, TG analysis, cyclic voltammetry, and single-crystal X-ray diffraction. Interestingly, a two-dimensional supramolecular network is constructed by the [PMo12O40]3− polyanions, [Ni(Dmf)3(H2O)]2+ cations, and water molecules via hydrogen-bonding interactions. The cyclic voltammetric measurements illustrate that the [PMo12O40]3− polyanion is the electrochemical redox active center of I in the solution.
Co-reporter:Junwei Zhao;Pengtao Ma;Jingping Wang;Jingyang Niu
Journal of Cluster Science 2009 Volume 20( Issue 4) pp:
Publication Date(Web):2009 December
DOI:10.1007/s10876-009-0270-5
Magnetic susceptibility investigations have been carried out on a family of the tetra-transition-metal sandwiched Weakley-type germanotungstates Na11H[Co4(H2O)2(α-GeW9O34)2]·31H2O (1), (C6N2H18)4[Co(H2O)6]H2[Co4(H2O)2(α-GeW9O34)2]·5.5H2O (2) and Na(H2O)2(C6N2H18)4.75H1.5[Ni4(H2O)2(α-GeW9O34)2]·1.5H2O (3) with the intention of studying the magnetic exchange properties of the rhomb-like four transition-metal ions in the central belt. The Co–Co and Ni–Ni ferromagnetic exchange interactions are dominant in the rhomb-like M4O16 units in 1–3. Furthermore, magnetic susceptibility measurements also reveal that the magnetic coupling constant J is a sensitive parameter that is closely realted to the M–O–M angles and M···M separations in the rhomb-like magnetic core. Variable-temperature ac susceptibilities exhibit that magnetic properties of 2 and 3 are related to the spin glassy behaviors.
Co-reporter:Jingping Wang, Suzhi Li, Yue Shen and Jingyang Niu
Crystal Growth & Design 2008 Volume 8(Issue 2) pp:372
Publication Date(Web):December 15, 2007
DOI:10.1021/cg070234v
A novel organic–inorganic heteropolyoxometalate compound [Cu2(2,2′-bipy)2(Inic)2(H2O)2][Y(Inic)2(H2O)5]H3[V2W18O62]·5.5H2O (1) was hydrothermally synthesized by reaction of Cu(CH3COO)2·4H2O, Y(NO3)3, V2O5, K9BW11O39, 2,2′-bipyridine, and γ-picolinic acid. The molecular asymmetric unit of 1 consists of one crystallographically independent heteropolyoxoanion [V2W18O62]6−, one dinuclear copper cation [Cu2(2,2′-bipy)2(Inic)2(H2O)2]2+, one nine-coordinated yttrium cation [Y(Inic)2(H2O)5]+, 5.5 water molecules of crystallization, and three protons based on charge balance. The polyoxoanion of 1 retains a classical Wells−Dawson structure. Unexpectedly, the Dawson-type anion with V atoms as heteroatoms has never been reported up to now.
Co-reporter:Jingping Wang, Pengtao Ma, Yue Shen and Jingyang Niu
Crystal Growth & Design 2008 Volume 8(Issue 9) pp:3130-3133
Publication Date(Web):July 26, 2008
DOI:10.1021/cg701278b
Four classic discrete Weakley-type sandwich germanotungstates, Na11H[Co4(H2O)2(α-GeW9O34)2]·31H2O (1), [Co(phen)3]4H3[Co3W(H2O)2(α-GeW9O34)2]·4H2O (2), (C6N2H18)4[Co(H2O)6]H2[Co4(H2O)2(α-GeW9O34)2]·5.5H2O (3), Na(H2O)2(C6N2H18)4.75H1.5[Ni4(H2O)2(α-GeW9O34)2]·1.5H2O (4), and two novel germanotungstates decorated by transition-metal complexes (C6N2H18)3H2[{Co(2,2′-bpy)}2Co4(H2O)2(α-GeW9O34)2]·4H2O (5) (2,2′-bpy = 2,2′-bipyridine), [Ag(phen)2]6H2[{Mn(phen)}2Mn4(H2O)2(α-GeW9O34)2]·3H2O (6) (phen = 1,10-phenanthroline) were synthesized hydrothermally and structurally characterized by elemental analyses, IR spectra, and single-crystal X-ray diffraction structural analysis. Compounds 1−4 show the classical tetra-transition-metal substituted Weakley-type sandwich structural frameworks, whereas 5 and 6 represent the new Weakley-type sandwich frameworks decorated by different transition-metal complexes. EPR studies at 110 K and room temperature reveal that the high-spin paramagnetic metal ions (Co2+, Mn2+) reside in octahedral geometry in 3 and 6, respectively.
Co-reporter:Jing-Ping WANG;Qing-Xia YAN;Xiao-Di DU
Chinese Journal of Chemistry 2008 Volume 26( Issue 7) pp:1239-1243
Publication Date(Web):
DOI:10.1002/cjoc.200890225
Abstract
Two germanotungstates based on the dysprosium cations and monovacant Keggin anions [GeW11O39]8−, [(CH3)4N]1.5H3.5[Dy(H2O)2(GeW11O39)]·1.5H2O (1) and [Cu(Hen)(en)]2[Cu(H2O)3]0.5{[Cu(H2en)(Hen)]-[Cu(H2O)3]0.5[Dy(GeW11O39)2]}·1.25H2O (2), have been synthesized and characterized by elemental analysis, inductively coupled plasma (ICP) analysis, IR spectroscopy, thermal analysis, and single-crystal X-ray diffraction. Crystal data for 1: monoclinic, space group C2/c with cell dimensions of a=2.8201(5) nm, b=2.2885(3) nm, c=2.4033(4) nm, β=123.875(2)°, V=12.878(4) nm3, Z=8, µ=21.239 mm−1; and for 2: monoclinic, space group P21/n with cell dimensions of a=2.12808(5) nm, b=1.63834(4) nm, c=3.18074(4) nm, β=93.760(2)°, V=11.0658(5) nm3, Z=4, µ=24.803 mm−1. The Dy3+/[GeW11O39]8− ratio of compound 1 is 1:1, and it displays an interesting one dimensional chainlike arrangement. And the Dy3+/[GeW11O39]8− ratio of compound 2 is 1:2 , and it shows a typical dimeric structure.
Co-reporter:Jingping WANG, Wei WANG, Qingxia YAN, Jingyang NIU
Journal of Rare Earths 2008 Volume 26(Issue 5) pp:638-642
Publication Date(Web):October 2008
DOI:10.1016/S1002-0721(08)60152-0
A novel double 1:11 series arsenotungstate, [CuI(phen)2]5H6[Sm(AsW11O39)2]·6H2O (phen=1,10-phenanthroline) was synthesized by the hydrothermal method and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. The title compound was monoclinic, space group P21/c, a=3.75710(2) nm, b=1.39776(8) nm, c=3.33735(18) nm, β =96.967(10)°, V=17.3969(17) nm3, Z=4. Single crystal X-ray structural analyses revealed that the dimeric polyanion, [SmAs2W22O78]1–, consisted of one central Sm3+ ion and two tetradentate heteropoly ligands [AsW11O39]7–. The Sm3+ ion and two tetradentate defective [AsW11O39]7– anions were joined together by the sharing of four oxygen atoms from each heteropoly ligand. The bond valence sum (BVS) calculations of the title compound suggested that all four Cu atoms were in the +1 oxidation sate.
Co-reporter:Jing-Ping Wang, Hong-Yu Niu, Jing-Yang Niu
Inorganic Chemistry Communications 2008 Volume 11(Issue 1) pp:63-65
Publication Date(Web):January 2008
DOI:10.1016/j.inoche.2007.10.015
A novel polyoxoniobate derivative {Nb6O19[Cu(2,2′-bipy)]2[Cu(2,2′-bipy)2]2} · 19H2O 1 has been synthesized in aqueous solution and characterized by single-crystal X-ray diffraction method, IR spectroscopy. The structure analysis indicates that the Lindqvist polyoxoniobate [Nb6O19]8− is capped by two divalent Cu atoms through three bridging oxygen atoms on two opposite {Nb3O3} groups and supports two [Cu(2,2′-bipy)2] fragments via the terminal oxygen atoms which are also located in opposite orientations.A novel polyoxoniobate derivative Nb6O19[Cu(2,2′-bipy)]2[Cu(2,2′-bipy)2]2 · 19H2O 1 has been synthesized in aqueous solution and characterized by single-crystal X-ray diffraction method and IR spectroscopy. The structure analysis indicates that the Lindquist polyoxoniobate [Nb6O19]8− is capped by two divalent Cu atoms through three bridging oxygen atoms on two opposite {Nb3O3} group and supports two [Cu(2,2′-bipy)2] fragments via the terminal oxygen atoms which are also located in opposite orientations.
Co-reporter:Jingping Wang, Guoqian Zhang, Pengtao Ma, Jingyang Niu
Inorganic Chemistry Communications 2008 Volume 11(Issue 7) pp:825-828
Publication Date(Web):July 2008
DOI:10.1016/j.inoche.2008.03.037
The first example of disubstituted Lindqvist-type polyoxomolybdate {[V(2,2-bipy)2]2(4,4-bipy)[Te2Mo4O19]} has been synthesized hydrothermally and characterized by elemental analyses, XPS, IR, TG-DTA and X-ray single crystal diffraction. The structural analysis shows that the neutral molecular unit [V(2,2-bipy)2]2[Te2Mo4O19] consists of a novel Lindqvist-type polyanion [Te2Mo4O19]6− supporting two vanadyl moieties [V(2,2-bipy)2]3+, and such neutral molecules are joined together by π − π stacking interactions between the pyridine groups to form a two-dimensional grid-like network with non-coordinating “guest” 4,4-bipys encapsulated.The first example of disubstituted Lindqvist-type polyoxomolybdate {[V(2,2-bipy)2]2(4,4-bipy)[Te2Mo4O19]} has been synthesized hydrothermally, which consists of a novel Lindqvist-type polyanion [Te2Mo4O19]6− supporting two vanadyl moieties [V(2,2-bipy)2]3+, and a non-coordinating “guest” 4,4-bipys molecule.
Co-reporter:Jing-ping Wang, Qing-xia Yan, Xiao-di Du, Xian-ying Duan, Jing-yang Niu
Inorganica Chimica Acta 2008 Volume 361(9–10) pp:2701-2706
Publication Date(Web):27 June 2008
DOI:10.1016/j.ica.2008.01.034
Three new polyoxometalate compounds based on the lacunary Keggin anion [α-GeW11O39]8− and the rare earth cations (Ln = NdIII, EuIII, TbIII), [(CH3)4N]2.5H7.5[Eu(GeW11O39)(H2O)2]2 · 4.5H2O (1), [(CH3)4N]2H8[Tb(GeW11O39)(H2O)2]2 · 2.5H2O (2) and [Nd0.5(H2O)2]H0.5[Nd2(GeW11O39)(DMSO)2(H2O)8] · 5.5H2O (3), have been synthesized and characterized by elemental analysis, inductively coupled plasmas (ICP) analysis, IR spectroscopy, single-crystal X-ray diffraction. The solid-state structures of compounds 1 and 2 consist of one-dimensional linear wires built of [α-GeW11O39]8− anions connected by Eu3+/Tb3+ cations, while in compound 3, the introduction of the organic molecules DMSO (DMSO = dimethyl sulphoxide) leads to a double-parallel chainlike structure constructed by two linear wires {[Nd(1)(GeW11O39)(DMSO)(H2O)2]5−}n linked by Nd3+ coordination cation. Furthermore, the luminescent property of compound 1 and the thermal stability of compound 3 were also studied.Three new polyoxometalate compounds based on the lacunary Keggin anion [α-GeW11O39]8− and the rare earth cations (Ln = NdIII, EuIII, TbIII), [(CH3)4N]2.5H7.5[Eu(GeW11O39)(H2O)2]2 · 4.5H2O (1), [(CH3)4N]2H8 [Tb(GeW11O39)(H2O)2]2 · 2.5H2O (2) and [Nd0.5(H2O)2]H0.5[Nd2(GeW11O39) (DMSO)2(H2O)8] · 5.5H2O (3), have been synthesized and characterized by elemental analysis, inductively coupled plasmas (ICP) analysis, IR spectroscopy, single-crystal X-ray diffraction. The solid-state structures of compounds 1 and 2 consist of one-dimensional linear wires built of [α-GeW11O39]8− anions connected by Eu3+/Tb3+cations, while in compound 3, the introduction of the organic molecules DMSO (DMSO = dimethyl sulphoxide) leads to a double-parallel chainlike structure constructed by two linear wires {[Nd(1)(GeW11O39)(DMSO)(H2O)2]5−}n linked by Nd3+ coordination cation.
Co-reporter:Qiu-xia HAN, Chun-zhang WANG, Jian-ru MA, Jing-yang NIU, Jing-ping WANG
Chemical Research in Chinese Universities 2008 Volume 24(Issue 3) pp:255-259
Publication Date(Web):May 2008
DOI:10.1016/S1005-9040(08)60054-9
Abstract
The reaction of α-H3[PW12O40] with Y(NO3)3 in the presence of DMF or DMSO leads to two complexes with the formulae {Y(DMSO)7}·PW12O40(1) and {[Y(DMF)7]2PW12O40}·PW12O 40(2). The crystal structures indicate that complex 1 consists of discrete [YLn]3+ cations and α-Keggin heteropolyanions [PW12O40]3−, whereas, in complex 2, donor-acceptor interaction results in a cation-anion-cation triplet. In addition, the electrochemical behavior of the two complexes indicates the usual successive reduction processes of the W atoms in the anions.
Co-reporter:Jing-Ping Wang ;Peng-Tao Ma;Jie Li;Hong-Yu Niu
Chemistry – An Asian Journal 2008 Volume 3( Issue 5) pp:822-833
Publication Date(Web):
DOI:10.1002/asia.200700363
Abstract
Rational self-assembly of Sb2O3 and Na2WO4, or (NH4)18[NaSb9W21O86] with transition-metal ions (Mn2+, Cu2+, Co2+), in aqueous solution under controlled conditions yield a series of sandwich type complexes, namely, Na2H2[Mn2.5W1.5(H2O)8(B-β-SbW9O33)2]⋅32 H2O (1), Na4H7[Na3(H2O)6Mn3(μ-OAc)2(B-α-SbW9O33)2]⋅20 H2O (OAc=acetate anion) (2), NaH8[Na2Cu4Cl(B-α-SbW9O33)2]⋅21 H2O (3), Na8K[Na2K(H2O)2{Co(H2O)}3(B-α-SbW9O33)2]⋅ 10 H2O (4), and Na5H[{Co(H2O)2}3W(H2O)2(B-β-SbW9O33)2]⋅11.5 H2O (5). These structures are determined by using the X-ray diffraction technique and further characterized by obtaining IR spectra and performing elemental analysis. Structure analysis reveals that polyoxoanions in 1 and 5 comprise of two [B-β-SbW9O33]9− building units, whereas 2, 3, and 4 consist of two isomerous [B-α-SbW9O33]9− building blocks, which are all linked by different transition-metal ions (Mn2+, Cu2+, or Co2+) with different quantitative nuclearity. It should be noted that compound 2 represents the first one-dimensional sinusoidal chain based on sandwich like tungstoantimonate building blocks through the carboxylate-bridging ligands. Additionally, 3 is constructed from sandwiched anions [Na2Cu4Cl(B-α-SbW9O33)2]9− linked to each other to form an infinitely extended 2D network, whereas 5 shows an interesting 3D framework built up from offset sandwich type polyoxoanion [{Co(H2O)2}3W(H2O)2(B-β-SbW9O33)2]6− linked by Co2+ and Na+ ions. EPR studies performed at 110 K and room temperature reveal that the metal cations (Mn2+, Cu2+, Co2+) reside in a square-pyramidal geometry in 2, 3, and 4. The magnetic behavior of 1–4 suggests the presence of weak antiferromagnetic coupling interactions between magnetic metal centers with the exchange integral J=−0.552 cm−1 in 2.
Co-reporter:Jing-Ping Wang;Hong-Yu Niu
Journal of Chemical Sciences 2008 Volume 120( Issue 3) pp:309-313
Publication Date(Web):2008 May
DOI:10.1007/s12039-008-0053-9
An inorganic-organic hybrid polyoxoniobate compound [Cu(en)2]3[Cu(en)2(H2O)]1·5 [K0·5Nb24O72H14·5]2·25H2O (1) was synthesized by reaction of K7HNb6O19·13H2O, Cu(CH3COOH)2·H2O and en (ethylenediamine) in aqueous solution and characterized by IR, ESR spectroscopy and single-crystal X-ray diffraction method. Structure analysis indicates that compound 1 consists of a new type polyoxoniobate anion [K0·5Nb24O72H14·5]9−, three [Cu(en)2]2+, one point five [Cu(en)2(H2O)]2+, and two point two five crystal water molecules. The structure contains N-H⋯O hydrogen bonds between the coordinated ethylenediamine and the polyniobate-anion. The whole molecule possesses the C3v symmetry.
Co-reporter:Jing-Ping Wang;Qing-Xia Yan;Xiao-Di Du
Journal of Cluster Science 2008 Volume 19( Issue 3) pp:491-498
Publication Date(Web):2008 September
DOI:10.1007/s10876-008-0191-8
A novel germanotungstate derivative based on the dysprosium cation and monovacant Keggin anion, [Cu(en)2]2[Cu(en)2(H2O)]2H3{[Cu(en)2]2[Na2(H2O)1.75][K(H2O)3][Dy2(H2O)2(GeW11O39)3]} · 6H2O(en = ethylenediamine) 1, has been synthesized by hydrothermal method and characterized by elemental analysis, IR-UV spectroscopy, thermal analysis and single-crystal X-ray diffraction. In the compound, one kind of clusters with the Dy3+/[GeW11O39]8− ratio of 2:3 was observed. Especially, the 2:3 type displays the novel cluster based on the rare earth and monolacunary Keggin polyoxometalate.
Co-reporter:Jing-Ping Wang, Xiao-Di Du, Jing-Yang Niu
Journal of Solid State Chemistry 2007 Volume 180(Issue 4) pp:1347-1352
Publication Date(Web):April 2007
DOI:10.1016/j.jssc.2007.02.004
A one-dimensional coordination polymer [Cu(en)2]2[Cu(en)2(H2O)]2{[Cu(en)2]2[Cu2Si2W22O78]}·4.5H2O (en=ethylenediamine), which represents the first example of one-dimensional organic–inorganic hybrid based on the bimolecular Keggin polyoxometalates {[Cu(en)2]2[Cu2Si2W22O78]}8− has been hydrothermally synthesized and characterized by elemental analyses, IR, TG and single crystal X-ray diffraction. Crystal data: C24H85Cu8N24O84.5Si2W22, monoclinic, P21/c, a=18.8126(3), b=23.0896(4), c=26.0711(4) Å, β=96.3790(10)°, V=11254.5(3) Å3, T=293(2) K; Z=4, μ=23.983 mm−1, R1=0.0628, wR2=0.1210 [I>2σ], R1=0.0854, wR2=0.1285 (all data ).A one-dimensional coordination polymer which represents the first example of 1D organic-inorganic hybrid based on the bimolecular Keggin POMs {[Cu(en)2]2[Cu2Si2W22O78]}8− has been hydrothermally synthesized and characterized.
Co-reporter:JingPing Wang;PengTao Ma;JingYang Niu
Science China Chemistry 2007 Volume 50( Issue 6) pp:784-789
Publication Date(Web):2007 December
DOI:10.1007/s11426-007-0140-7
A new organic-inorganic hybrid polyoxometalate based on Dawson-like polyoxotungstate anion [SbW18O60]9−, formulated [Co(2,2′-bpy)3]2[Co(2,2′-bpy)2Cl][Co(2,2′-bpy)2]H2[SbW18O60]·4H2O (2,2′-bpy=2,2′-bipyridine) has been synthesized from Sb2O3, Na2WO4, CoCl2, and 2,2′-bipyridine materials by hydrothermal method, and which was characterized by elemental analyses, IR, XPS, EPR, TG, and X-ray single crystal diffraction. Structure analysis shows that the polyoxoanion self-assembled under hydrothermal conditions consists of a Dawson-like polyoxotungstate cluster anion [SbW18O60]9− encapsulating capsulating a pyramidal {SbO3{ group within the {W18{ cluster cage. EPR spectra show that the high-spin octahedral Co∥ and low-spin Co∥ ions coexist in the title compound. Magnetic properties indicate that the compound is antiferromagnetic.
Co-reporter:Jing-Yang Niu;Mei-Lin Wei;Jing-Ping Wang;Dong-Bin Dang
European Journal of Inorganic Chemistry 2004 Volume 2004(Issue 1) pp:
Publication Date(Web):23 OCT 2003
DOI:10.1002/ejic.200300048
The structures of three 1:1 composite compounds prepared with the polyoxometalate (POM) [PMo12O40]3− and the cations [Ln(NMP)6]3+ [Ln = La (1), Ce (3), Pr (2); NMP = N-methyl-2-pyrrolidone] exhibit two types of zig-zag chains with alternating cations and anions through Mo−Ot−Ln−Ot−Mo links in the crystal. The compounds were characterized by IR, UV, and ESR spectroscopy, single-crystal X-ray structural analysis, and by a study of their thermal properties. In all the compounds, the La3+, Pr3+, and Ce3+ centers are eight-coordinate with the oxygen atoms in bicapped trigonal-prismatic geometries. The variation of the average Ln−O separations along the La, Ce, and Pr series is consistent with the effects of the lanthanide contraction. The results of the single-crystal X-ray diffraction analyses and the IR spectroscopic studies are in agreement and both show the metal cation units are coordinatively bonded to the Keggin clusters. The UV spectra of the title compounds suggest that their structures are entirely disrupted in dilute solution. Low-temperature ESR spectra indicate that thermal electron delocalization occurs among the Mo atoms in the three compounds. The results of cyclic voltammetry (CV) show that compounds 1, 2, and 3 all undergo five two-electron reversible reductions and that the [PMo12O40]3− anions are the active centers for electrochemical redox reactions in solution, while the corresponding cations have only a small effect on the electrochemical properties. Studies of magnetic properties show that 1 is diamagnetic, while 2and 3 exhibit antiferromagnetic Pr−Pr or Ce−Ce exchange interactions. In addition to the results of CV, the average bond lengths and the magnetic properties of compound 3 indicate that the oxidation state of cerium is III in the compound of formula [{Ce(NMP)6}(PMo12O40)]n. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Co-reporter:Jingyang Niu, Dongjie Guo, Junwei Zhao and Jingping Wang
New Journal of Chemistry 2004 vol. 28(Issue 8) pp:980-987
Publication Date(Web):07 Jul 2004
DOI:10.1039/B401769B
Three polyoxometalate-based composite compounds containing zero-dimensional cross-like and one-dimensional chain-like structures, [Gd(DMF)6(H2O)2]2·[P2W18O62]·4DMF·2H2O (1), [Ce(NMP)3(H2O)5][Ce(NMP)3(H2O)4][(P2W18O62)]·4H2O (2) and [{Gd(DMF)6}{Gd(DMF)7}(P2W18O62)]·0.5DMF (3), were constructed from octadecatungstodiphosphorate clusters interacting with [RE(donor)]3+ [RE=Gd(III), Ce(III); donor=DMF (N,N-dimethylformamide), NMP (N-methyl-2-pyrrolidone)] groups. Single crystal X-ray structural analyses reveal that, for compound 1, the interactions between the polyanions and the charge compensating cations are mainly hydrogen bonds, van der Waals forces and electrostatic forces; for compound 2, two terminal oxygen (Ot) atoms located in “belt” sites of the polyanion are coordinated by RE cations, which generates an unprecedented zero-dimensional isolated structure; for compound 3, the adjacent polyanions are polymerized to form a one-dimensional infinite linear chain by the bridging RE coordination cations and exhibit the type –ACACAC–. The apparent difference in the ESR spectra of the two compounds containing Gd(III) ions seems to be related to different coordination environments of the Gd(III) ions. Thermal analyses show that the frameworks of the polyanions decompose at 611, 615 and 602°C in compounds 1–3, respectively, and the stability of polyanions in compounds 1–3 is much stronger than that in the parent acid.
Co-reporter:Jingyang Niu, Junwei Zhao, Jingping Wang, Pengtao Ma
Journal of Molecular Structure 2004 Volume 699(1–3) pp:85-92
Publication Date(Web):2 August 2004
DOI:10.1016/j.molstruc.2004.05.005
A novel two-dimensional infinite network organic–inorganic hybrid neodymium(III)-centered compound of formula (dmaH)2[Nd(dmf)4(H2O)][α-BW12O40]·H2O (1) [dma=dimethylamine and dmf=N,N-dimethylformamide] is obtained by the conventional self-assembly reaction of neodymium oxide, N,N-dimethylformamide and borotungstic acid (α-H5BW12O40·30H2O) in the mixed solvent of acetonitrile and water, and characterized by IR, UV–visible spectra and X-ray single crystal diffraction. Structural analysis indicates that every [α-BW12O40]5− polyanion interconnects with three adjacent [Nd(dmf)4(H2O)]3+ subunits by means of W–O–Nd bridges, meanwhile, every [Nd(dmf)4(H2O)]3+ building block is surrounded by three neighboring [α-BW12O40]5− polyanions by making use of which an unprecedented two-dimensional extended network structure can be constructed. Interestingly, this structure pattern may act as useful model for the design and assembly of functional molecule-based compounds, especially in the field of molecular sieve materials.
Co-reporter:Jingyang Niu, Junwei Zhao, Jingping Wang
Journal of Molecular Structure 2004 Volume 701(1–3) pp:19-24
Publication Date(Web):1 September 2004
DOI:10.1016/j.molstruc.2004.05.013
A Keggin-type monovacant silicotungstate derivative K2H2{Er(H2O)6[Er(H2O)3SiW11O39]}2·22H2O (1) has been synthesized by reaction of the polyoxometalate α-K8SiW11O39·13H2O ligands with erbiumIII cations in the aqueous solution under moderate condition, and characterized by elemental analyses, IR, UV-visible spectroscopy and X-ray single-crystal diffraction. Crystal data: K2H2{Er(H2O)6[Er(H2O)3SiW11O39]}2·22H2O, triclinic, P−1, a=12.463(3), b=14.849(3), c=16.772(3) Å, α=95.37(3), β=94.65(3), γ=106.76°, Z=1, R1=0.0638, wR2=0.1140. X-ray single-crystal diffraction reveals that the polyanion of crystalline 1 is made up of two crystallographically identical polyoxometalate-based {Er(H2O)6[Er(H2O)3SiW11O39]}2− building block units, which are linked through erbium centers by means of the terminal oxygen atoms from the backbone of precursor [α-SiW11O39]8−, generating a novel 1D chain-like structure. Variable-temperature magnetic susceptibility study indicates the presence of the relatively strong spin-orbital coupling in compound 1 in the wide temperature region of 70–300 K.
Co-reporter:Jingyang Niu, Junwei Zhao, Dongjie Guo, Jingping Wang
Journal of Molecular Structure 2004 Volume 692(1–3) pp:223-229
Publication Date(Web):5 April 2004
DOI:10.1016/j.molstruc.2004.02.002
The heteropolyanion [Yb(α-2-P2W17O61)2]17− has been isolated as a potassium salt in ∼30% yield by five-day decreasing temperature-programmed from 60 °C to room temperature, in a potassium acetate buffer, formed by reaction of K6P2W18O62·10H2O with Yb(NO3)3 and characterized by IR, UV spectra. Single crystal X-ray structural analysis of K16H[Yb(α-2-P2W17O61)2]·44H2O (triclinic, space group PI a=14.499(3), b=22.433(5), c=24.505(5) Å, α=95.36(3),β=102.67(3), γ=100.06(3)°, Z=2, 24,089 independent reflections, R1=0.0497) reveals that two chemically identical [α-2-P2W17O61]10− moieties are connected through one Yb atom, which is in a square antiprismatic coordination environment with eight oxygen atoms, four from each of the two [α-2-P2W17O61]10− moieties. The Yb(III) ion substitutes for two [W=O]4+ units in the ‘cap’ regions of the tungsten–oxygen frameworks of the two parent Wells–Dawson ions. The point group symmetry of the title polyanion is C2. In the extensive pH region from 10.5 to 1.60, the cyclic voltammograms for the title compound in the presence of 0.5 M NaCl aqueous solution as supporting electrolyte mainly illustrate nearly reversible one-electron reduction processes. The results of the thermogravimetric analysis of the title compound show one one-step slow weight loss and the framework decomposition of the polyanion in the title compound is at 560.0 °C.
Co-reporter:Jing-Yang Niu, Zi-Liang Wang, Jing-Ping Wang
Journal of Solid State Chemistry 2004 Volume 177(Issue 10) pp:3411-3417
Publication Date(Web):October 2004
DOI:10.1016/j.jssc.2004.06.001
Two kinds of complexes [Ni(DETA)2]3[SiNiW11O39]·2.5H2O (DETA=diethylenetriamine) (1) and [H2en]2[Ba0.15(H2O)2(Hen2)]H1.7[SiNaW11O39]·2H2O (2) were obtained from the hydrothermal reaction and characterized by single crystal X-ray diffraction analysis and IR spectra. Crystal data: C24H83N18Ni4O41.5SiW11 (1), monoclinic, Pn, a=10.926(2) Å, b=23.022(5) Å, c=13.221(3) Å, β=94.27(3)°, V=3316.4(11) Å3, Z=2; C8H46.7N8Ba0.15NaO43SiW11 (2), monoclinic, P21, a=12.840(3) Å, b=11.174(2) Å, c=16.693(3) Å, β=91.14(3)°, V=2394.4(8) Å3, Z=2. Both of them consists of one mono-substituted Keggin unit [SiMW11O39](8−n)− (MNi, Na, n=2, 1) obtained by metal atom substituting for a W atom from the plenary anion [SiW12O40]4−. This unit then connects with other adjacent units via M–O–W bridges constructing an infinitely one-dimensional chain-like structure in which the metal cation and polyanion alternate. Moreover, both of Ni or Na atoms are in a distorted octahedral environment with six oxygen atoms and occupy one position in the oxometalate shell of the Keggin structure.
Co-reporter:Jingping Wang, Junwei Zhao, Jingyang Niu
Journal of Molecular Structure 2004 Volume 697(1–3) pp:191-198
Publication Date(Web):16 July 2004
DOI:10.1016/j.molstruc.2004.04.010
A novel 1D chain organic–inorganic polymer H1.5[Sm(H2O)8]0.5[Sm(DMF)6(H2O)(α-P2W18O62)]·DMF·3H2O with Dawson-type polyoxometalates as building blocks has been synthesized by reaction of SmCl3, DMF and α-H6P2W18O62·nH2O in the mixed solution of acetonitrile and water in the bulk ratio of 1:1 and characterized by IR, UV spectra, TG-DTA technique, electrochemical behavior and X-ray single-crystal diffraction. X-ray single-crystal structural analysis displays that the title compound crystallizes in an orthorhombic lattice, P21212 space group, with a=23.605(5), b=30.443(6), c=14.536(3) Å, α=β=γ=90°, V=10446(4) Å3, Z=4, R1=0.0493, wR2=0.0783. [Sm(1)(DMF)6(H2O)]3+ coordination cation is nine-coordinate with a distorted tricapped trigonal prismatic environment, which is bridged through W–O–Sm(1)–O–W linkages to build an unprecedented 1D zigzag linear chain structure by alternate polyoxometalate anions and metal coordination cations in the polymer, whereas [Sm(2)(H2O)8]3+ coordination ion is a discrete unit incorporated into the gaps of the polyoxoanions with an eight-coordinate square antiprismatic geometry. Cyclic voltammetry reveals that the pH of the supporting electrolytic solution has a marked effect on the electrochemical behaviors.
Co-reporter:Jingyang Niu, Mingxue Li, Jingping Wang
Journal of Organometallic Chemistry 2003 Volume 675(1–2) pp:84-90
Publication Date(Web):30 May 2003
DOI:10.1016/S0022-328X(03)00252-3
In the presence of NBu4nBr acting as phase-transfer reagent, organosilicon trichloride RSiCl3 reacts in acetonitrile with the trivacant tungstophosphate sodium salt β-A-Na8H[PW9O34]·24 H2O to give hybrid organosilyl polyoxotungstate derivatives α-A-[NBu4n]3[PW9O34(RSiO)3(RSi)] (R=C2H3 (1), CH3 (2)). These compounds are characterized by X-ray crystallography. Each of the two hybrid anions consists of one α-A-PW9O349− framework on which is grafted by three RSiO groups through six SiOW bridges, each of which is attached to the fourth RSi through three SiOSi bridges. Both hybrid anions become saturated, close cage structure and display C3v symmetry.In the presence of NBu4nBr acting as phase-transfer reagent, organosilicon trichloride RSiCl3 reacts in acetonitrile with the trivacant tungstophosphate sodium salt β-A-Na8H[PW9O34]·24 H2O to give hybrid organosilyl polyoxotungstate derivatives α-A-[NBu4n]3[PW9O34(RSiO)3(RSi)] (R=C2H3 or CH3). Their crystal structures are determined by X-ray single crystal diffraction analysis.
Co-reporter:Jingyang Niu, Junwei Zhao, Jingping Wang, Mingxue Li
Journal of Molecular Structure 2003 Volume 655(Issue 2) pp:243-250
Publication Date(Web):29 July 2003
DOI:10.1016/S0022-2860(03)00284-9
In the presence of NBu4nBr acting as phase-transfer reagent, organosilicon trichloride C2H5SiCl3 reacts in acetonitrile with the trivacant tungstophosphate sodium salt β-A-Na8H[PW9O34]·24H2O to give hybrid organosilyl polyoxotungstate derivative α-A-[NBu4n]3[PW9O34(C2H5SiO)3(C2H5Si)]. X-ray single crystal structural analysis indicates that the title compound is monoclinic, space group Cc, with lattice constants a=26.828(5), b=22.459(5), c=17.517(4) Å, β=103.19(3)°, V=10,276(4) Å3, Z=4, R=0.0462. According to the result of X-ray single crystal diffraction and chemical analysis, the hybrid polyanion consists of one α-A-[PW9O34]9− framework on which are grafted simultaneously three RSiO groups through six Si–O–W bridge bonds, each of which is attached to the fourth RSi group through three Si–O–Si bridge bonds. The hybrid polyanion becomes a partial saturated, closed cage structure and also has an assembly of virtual C3V symmetry.
Co-reporter:Jing-Yang Niu, Mei-Lin Wei, Jing-Ping Wang, Dong-Bin Dang
Journal of Molecular Structure 2003 Volume 655(Issue 1) pp:171-178
Publication Date(Web):15 July 2003
DOI:10.1016/S0022-2860(03)00285-0
A novel compound, [{Gd(NMP)6}(PMo12O40)]n, has been synthesized and characterized by IR, and UV spectroscopy, and single crystal X-ray structural analysis. It forms an unprecedented one-dimensional zigzag chain built from alternating polyanions and cationic units through Mo–Ot–Gd–Ot–Mo links in the crystal. In the compound, Gd3+ is eight-coordinated with a bicapped trigonal prism geometry environment of oxygen atoms. The results of the single crystal X-ray diffraction analyses and IR are agreement and both show the metal cation units are coordinately bonded to the Keggin cluster. The UV spectrum of the title compound suggests that the compound is entirely dissociated in dilute solution.
Co-reporter:Jingping Wang, Junwei Zhao, Pengtao Ma, Junchuang Ma, Linping Yang, Yan Bai, Mingxue Li and Jingyang Niu
Chemical Communications 2009(Issue 17) pp:NaN2364-2364
Publication Date(Web):2009/03/27
DOI:10.1039/B822368H
A novel type of heteropolyoxoanion (HPOA) precursors {[Ca (H2O)]6[P4M6O34]2}12− [M = WVI (1), MoVI (2)] has been synthesized and structurally characterized, which represents the rare membership of the HPOA family constituted by two early-transition-metal clusters ([P4M6O34]12−) and a main-group metal cluster of high nuclearity ([Ca6]12+).
Co-reporter:Jie Li, Jipeng Guo, Jiage Jia, Pengtao Ma, Dongdi Zhang, Jingping Wang and Jingyang Niu
Dalton Transactions 2016 - vol. 45(Issue 15) pp:NaN6731-6731
Publication Date(Web):2016/03/01
DOI:10.1039/C6DT00352D
A novel isopentatungstate-supported metal carbonyl derivative KH[(CH3)4N]3{[Re(CO)3]4[(μ2-OH)(μ3-O)(W5O18)]}·6H2O (1) has been synthesized and characterized. Compound 1 represents the second example of isopolyoxotungstate-supported metal carbonyl derivative. The catalysis of 1 for alkene epoxidation with H2O2 was investigated, and was found to efficiently catalyze the epoxidation of cyclooctene with high conversion (98.9%) and excellent selectivity (99%). Furthermore, the solution behavior of the polyanion 1 was also explored using electrospray ionization mass spectrometry.
Co-reporter:Dongdi Zhang, Juan Zhao, Yanhui Zhang, Xiaojing Hu, Longsheng Li, Pengtao Ma, Jingping Wang and Jingyang Niu
Dalton Transactions 2013 - vol. 42(Issue 8) pp:NaN2699-2699
Publication Date(Web):2013/01/07
DOI:10.1039/C2DT32678G
Two novel octamolybdate-based tricarbonyl metal derivatives have been successfully synthesized and characterized, which represent the first two examples of tricarbonyl metal groups attached to a new {Mo8O30} building block.
Co-reporter:Nan Zhang, Yanxue Tai, Mingxue Li, Pengtao Ma, Junwei Zhao and Jingyang Niu
Dalton Transactions 2014 - vol. 43(Issue 13) pp:NaN5189-5189
Publication Date(Web):2014/01/10
DOI:10.1039/C4DT00077C
Up to now, the metal complexes with thiocarbonohydrazones have been comparatively rare. Herein, three main group monometallic complexes formulated as [Bi(HL)(NO3)2(H2O)] (1), [Ga(HL)2]OAc·EtOH (2) and [(Ph)2Sn(HL)(OAc)]·DMF (3), where H2L = bis(2-acetylpyrazine)thiocarbonohydrazone, have been synthesized and characterized. The crystal structures of complexes 2 and 3 have been determined by single-crystal X-ray diffraction. Growth inhibition assays have indicated that both the free ligand and the title complexes are capable of inhibiting cell proliferation growth and could slightly distinguish the human hepatocellular carcinoma HepG2 cells from normal hepatocyte QSG7701 cells. Of particular note is the fact that the bismuth(III) complex 1 is the most active compound of this study and is 14-fold more cytotoxic than H2L with an IC50 value of 2.96 ± 0.25 μM. Its possible apoptotic mechanism has been evaluated in HepG2 cells. Complex 1 promotes a dose-dependent apoptosis in HepG2 cells and the apoptosis is associated with an increase in intracellular reactive oxygen species (ROS) production and reduction of mitochondrial membrane potential (MMP).
Co-reporter:Qiaohua Geng, Qisen Liu, Pengtao Ma, Jingping Wang and Jingyang Niu
Dalton Transactions 2014 - vol. 43(Issue 26) pp:NaN9846-9846
Publication Date(Web):2014/04/29
DOI:10.1039/C4DT00875H
An unprecedented arsenic-disubstituted Lindqvist-type peroxopolyoxoniobate Cs2.5Na2{As2Nb4(O2)4O14H1.5}·11H2O has been successfully synthesized and characterized. The photocatalytic activity of the cluster for H2 evolution from water is investigated by irradiating with a 300 W Xe lamp, which shows a certain photocatalytic water splitting activity.
Co-reporter:Juan Zhao, Junsheng Wang, Junwei Zhao, Pengtao Ma, Jingping Wang and Jingyang Niu
Dalton Transactions 2012 - vol. 41(Issue 19) pp:NaN5837-5837
Publication Date(Web):2012/03/26
DOI:10.1039/C2DT12130A
Two novel trivacant Keggin-type polyoxometallate-based manganese carbonyl derivatives K8[(OC)3Mn(A-α-H2GeW9O34)]·10H2O (1) and K8[(OC)3Mn(A-α-H2SiW9O34)]·11H2O (2) have been synthesized by degradation of the metastable [γ-XW10O36]8− (X = GeIV, SiIV) in CH3CN–H2O solvent (1:2, vol.) and structurally characterized by elemental analyses, IR spectra, thermogravimetric analysis, and single-crystal X-ray diffraction. X-ray diffraction analyses indicate that 1 and 2 are isomorphic and consist of a [(OC)3Mn]+ group and a trivacant [A-α-H2XW9O34]8− fragment, which exhibit the first examples of trivacant Keggin-type metal carbonyl derivatives. Additionally, the electrocatalytic properties of both for NO2− oxidation have been investigated.
Co-reporter:Suzhi Li, Dongdi Zhang, Yuan Yuan Guo, Pengtao Ma, Xiaoyang Qiu, Jingping Wang and Jingyang Niu
Dalton Transactions 2012 - vol. 41(Issue 33) pp:NaN9888-9888
Publication Date(Web):2012/05/23
DOI:10.1039/C2DT30517H
A novel strawberry-like organic–inorganic hybrid, {Na(H2O)3[Lu(pydc)(H2O)3]3}[SiW12O40]·26.5H2O (H2pydc = pyridine-2,6-dicarboxylate) containing an intriguing trinuclear lutetium cluster {Na(H2O)3[Lu(pydc)(H2O)3]3}4+ has been synthesized and its luminescent properties, IR, UV, TG, PXRD analyses and single crystal X-ray diffraction were investigated.
Co-reporter:Pengtao Ma, Feng Hu, Rong Wan, Yu Huo, Dongdi Zhang, Jingyang Niu and Jingping Wang
Journal of Materials Chemistry A 2016 - vol. 4(Issue 23) pp:NaN5433-5433
Publication Date(Web):2016/05/06
DOI:10.1039/C6TC00960C
A series of inorganic–organic hybrid double-tartaric bridging mono-lanthanide substituted phosphotungstates with a general formula of [N(CH3)4]6K3H7[Ln(C4H2O6)(α-PW11O39)]2·27H2O (Ln = Dy for 1Dy, Er for 2Er, and Yb for 3Yb) have been synthesized by the reactions of K14[P2W19O69(H2O)]·24H2O and LnCl3·6H2O in the presence of tartaric acid and tetramethyl ammonium counterions in an aqueous medium. Crystal structure analyses reveal that 1Dy–3Yb are isomorphic and are all built from two mono-lanthanide substituted Keggin polyoxoanion fragments joined together by two tartaric ligands. 1Dy–3Yb exhibit reversible photochromism and they can change from white (for 1Dy and 3Yb) or pink (for 2Er) to blue upon UV irradiation and then their colors gradually recover in the dark for about five days. The solid-state photoluminescence spectra of 1Dy–3Yb display their characteristic emissions of lanthanide components based on their 4f–4f transitions. Moreover, the fluorescence of 1Dy displays an effectively switchable behaviour when exposed to UV light, the intensity of the emission band at 573 nm gradually weakens as the irradiation time increases and the intensity drops to 2.4% of the original intensity after 30 minutes. It is noteworthy that the frequency dependence of the ac-susceptibility was found for 1Dy, suggesting a typical single-molecule magnet (SMM) behavior with an energy barrier of 20 K.
Co-reporter:Shumin Chen, Pengtao Ma, Huihui Luo, Yangyang Wang, Jingyang Niu and Jingping Wang
Chemical Communications 2017 - vol. 53(Issue 26) pp:NaN3712-3712
Publication Date(Web):2017/03/06
DOI:10.1039/C7CC00591A
A europium-containing isopolyoxoniobate with the formula (CN3H6)7K3H17{Eu3(H2O)9Nb48O138(H2O)6}·40H2O is synthesized under the protection of citric acid. ESI-MS spectra show that the polyoxoanion structural unit {Eu3(H2O)9[Nb48O138(H2O)6]}27− is intact in aqueous solution. Moreover, its solid-state luminescence displays a red emission with the long lifetime of 258 μs.
Co-reporter:Ran Ban, Xiaopeng Sun, Jiawei Wang, Pengtao Ma, Chao Zhang, Jingyang Niu and Jingping Wang
Dalton Transactions 2017 - vol. 46(Issue 18) pp:NaN5863-5863
Publication Date(Web):2017/03/28
DOI:10.1039/C7DT00615B
Four structurally intriguing members of a new family of lanthanide (Ln)-containing organophosphonate-functionalized polyoxotungstates with the general formula K2[Ln(H2O)4(AsW9O33)(W2O3)(O3PCOHCH3PO3)Ln(H2O)7]2·15H2O [Ln = Ce (1Ce), Nd (2Nd), Sm (3Sm) and Eu (4Eu)] were directly isolated by controlling the reaction parameters and well established by single-crystal X-ray diffraction, PXRD analyses, IR spectra, elemental analyses, TG and EDX analyses. All the four three-dimensional frameworks consist of the S-shaped inorganic building block {[(AsW9O33)(W2O3)]2}, two organophosphonate groups {O3PCOHCH3PO3} and four Ln ions. The magnetic properties of the four compounds and the solid-state photoluminescence properties of 2Nd, 3Sm, and 4Eu were also fully investigated.
Co-reporter:Rong Wan, Pengtao Ma, Mengdan Han, Dongdi Zhang, Chao Zhang, Jingyang Niu and Jingping Wang
Dalton Transactions 2017 - vol. 46(Issue 16) pp:NaN5405-5405
Publication Date(Web):2017/03/23
DOI:10.1039/C7DT00250E
Two novel trans-isomers of 1:2-type lanthanide-containing monolacunary Dawson-type tungstophosphates [Ln(α2-P2W17O61)2]17− (Ln = LaIII (1), CeIII (2)) were successfully isolated and characterized by elemental analysis, IR, TG, and 31P NMR studies. Both polyanions 1 and 2 consist of one Ln3+ ion sanwiched between two monolacunary Dawson-type tungstophosphates fragments [α2-P2W17O61]10− oriented at 180° with respect to each other. The solid-state and solution 31P NMR spectroscopy revealed that the trans-[Ce(α2-P2W17O61)2]17− species probably quickly isomerizes to the cis-isomer species in solution.
Co-reporter:Zhijie Liang, Ke Wang, Dongdi Zhang, Pengtao Ma, Jingyang Niu and Jingping Wang
Dalton Transactions 2017 - vol. 46(Issue 5) pp:NaN1371-1371
Publication Date(Web):2016/12/15
DOI:10.1039/C6DT04223F
A new heteropolyniobate, [Fe3Nb25O76]18−, persists in aqueous solution by means of electrospray ionization mass spectrometry. It has been synthesized and characterized by IR, TGA, EDX-SEM, magnetic and single-crystal X-ray diffraction, and it features an Fe-centred Nb-Keggin unit {Fe3Nb10}.
Co-reporter:Yanfen Liang, Suzhi Li, Donghui Yang, Pengtao Ma, Jingyang Niu and Jingping Wang
Journal of Materials Chemistry A 2015 - vol. 3(Issue 18) pp:NaN4639-4639
Publication Date(Web):2015/03/26
DOI:10.1039/C5TC00297D
A series of inorganic–organic hybrid heteropolyoxomolybdates built from [TeMo6O21]2− polyoxoanions and multicarboxylic acids including (C3N2H5)4H6[(TeMo6O21)2{O2C(CH2)2CO2}3]·9.5H2O (1), (C3N2H5)8H2[(TeMo6O21)2{O2C(CH2)6CO2}3]·3.5H2O (2) and (CN3H4)16H4[(TeMo6O21)4{C6H3(COO)3}4]·16H2O (3) have been synthesized arising from the reactions of (NH4)6Mo7O24·4H2O, Na2TeO3/TeO2 and the corresponding multicarboxylic acids in an aqueous medium. X-ray single crystal diffraction, X-ray powder diffraction (XPRD), elemental analyses, inductively coupled plasma (ICP) spectra, IR spectra, UV spectra and thermogravimetric (TG) analyses have been implemented. Crystal structure analyses reveal that both compounds 1 and 2 are dimers, while 3 is a tetramer, however, they contain the same {TeMo6} unit which consists of a six-membered MoO6 octahedral ring capped by one {TeO3} trigonal pyramid. Compounds 1–3 exhibit intriguing allochroic properties. They can change color from white to blue/green when heated. Upon the irradiation of a xenon lamp (full wave-band, P = 300 W), their color can change from white to reddish brown.
Co-reporter:Jingyang Niu, Linping Yang, Junwei Zhao, Pengtao Ma and Jingping Wang
Dalton Transactions 2011 - vol. 40(Issue 33) pp:NaN8300-8300
Publication Date(Web):2011/07/21
DOI:10.1039/C1DT11042J
Three novel octatungstate-supported tricarbonyl metal derivatives have been synthesized and characterized, which represent the first examples of isopolyoxotungstates-supported carbonyl metal compounds.
Co-reporter:Junwei Zhao, Dongying Shi, Lijuan Chen, Yanzhou Li, Pengtao Ma, Jingping Wang and Jingyang Niu
Dalton Transactions 2012 - vol. 41(Issue 35) pp:NaN10751-10751
Publication Date(Web):2012/07/17
DOI:10.1039/C2DT30949A
Three organic–inorganic hybrid copper–lanthanide heterometallic germanotungstates, {[Cu(en)2(H2O)] [Cu3Eu(en)3(OH)3(H2O)2](α-GeW11O39)}2·11H2O (1), {[Cu(en)2(H2O)][Cu3Tb(en)3(OH)3(H2O)2](α-GeW11O39)}2·11H2O (2) and {[Cu(en)2(H2O)][Cu3Dy(en)3(OH)3(H2O)2](α-GeW11O39)}2·10H2O (3) and three polyoxometalate hybrids built by lanthanide-containing germanotungstates and copper–ethylendiamine complexes, Na2H6[Cu(en)2(H2O)]8{Cu(en)2[La(α-GeW11O39)2]2}·18H2O (4), K4H2[Cu(en)2(H2O)2]5[Cu(en)2(H2O)]2[Cu(en)2]2{Cu(en)2[Pr(α-GeW11O39)2]2}·16H2O (5) and KNa2H7[enH2]3[Cu(en)2(H2O)]2[Cu(en)2]2{Cu(en)2[Er(α-GeW11O39)2]2}·15H2O (6) (en = ethylenediamine) have been hydrothermally synthesized and structurally characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP–AES) analyses, IR spectra, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS) and single-crystal X-ray diffraction. 1–3 are essentially isomorphous and their main skeletons display the interesting dimeric motif {[Cu3Ln(en)3(OH)3(H2O)2](α-GeW11O39)}24−, which is constructed from two {Cu3LnO4} cubane anchored monovacant [α-GeW11O39]8− fragments through two W–O–Ln–O–W linkers. The primary backbones of 4–6 exhibit the tetrameric architecture {Cu(en)2[Ln(α-GeW11O39)2]2}24− built by two 1:2-type [Ln(α-GeW11O39)2]13− moieties and one [Cu(en)2]2+ bridge, albeit they are not isostructural. To our knowledge, 1–6 are rare polyoxometalate derivatives consisting of copper–lanthanide heterometallic/lanthanide germanotungstate fragments. 1 exhibits antiferromagnetic coupling interactions within the {Cu3EuO4} cubane units, while 2 and 3 display dominant ferromagnetic interactions between the TbIII/DyIII and CuII cations. The room-temperature solid-state photoluminescence properties of 1–3 have been investigated.
Co-reporter:Suzhi Li, Yuan yuan Guo, Dongdi Zhang, Pengtao Ma, Xiaoyang Qiu, Jingping Wang and Jingyang Niu
Dalton Transactions 2012 - vol. 41(Issue 17) pp:NaN5240-5240
Publication Date(Web):2012/02/20
DOI:10.1039/C2DT12491B
Four di-CuII-substituted sandwich-type germanomolybdates, (H2en)2H7{[Na0.5(H2O)3.5]2[Cu2(β-Y-GeMo9O33)2]}·6H2O (1), (H2en)2H{[Na2.5(H2O)12]2[Cu(en)2][Cu2(β-Y-GeMo9O33)2]}·8H2O (2), [Na4(H2O)12]2H4[Cu2(β-Y-GeMo9O33)2]}·11H2O (3) and [Cu(en)2]2[Cu(en)2(H2O)]2{[Cu(en)2]2[Cu2(β-Y-GeMo9O33)2]}·8H2O (4) (en = ethylenediamine), have been prepared. It is interesting that 1–3 were obtained in the same aqueous solution reaction system but exhibited different structures: 1 displays a 0D structure, 2 shows an organic–inorganic 1D chain structure, while 3 displays a 2D network. 4 was synthesized under hydrothermal condition by the same reagents, which represents the first transition metal-sandwiched organic–inorganic 2D heteropolymolybdate.
Co-reporter:Ling Yang, Qisen Liu, Pengtao Ma, Jingyang Niu and Jingping Wang
Dalton Transactions 2015 - vol. 44(Issue 30) pp:NaN13472-13472
Publication Date(Web):2015/06/26
DOI:10.1039/C5DT00262A
An unprecedented silicotungstate trimer K9[H14{SiW10MnIIMnIIIO38}3(CO3)]·39H2O (1) has been successfully synthesized, in which the CO32− resides inside the three Keggin {SiW10MnIIMnIIIO38} units and the three O atoms serve as μ2-O atoms to connect with three MnIII. Magnetic investigation indicates that 1 exhibits antiferromagnetic coupling.
Co-reporter:Xiang Ma, Pengtao Ma, Dongdi Zhang, Jiai Hua, Chao Zhang, Tengfei Huang, Jingping Wang and Jingyang Niu
Dalton Transactions 2013 - vol. 42(Issue 4) pp:NaN878-878
Publication Date(Web):2012/11/12
DOI:10.1039/C2DT32061D
A cage-like {[Ca(H2O)]6(H2O)}12+ cluster with a water molecule enwrapped, sandwiched by two novel [As4W6O34]12− fragments, has been obtained, and the extension of these clusters from molecules into a 2-D layer occurs through [Ca(H2O)5]2+ linkers, which represents the first heteropolyoxoanion (HPA) constituted by [As4W6O34]12− and the unprecedented high nuclearity {[Ca(H2O)]6(H2O)}12+ cluster.
Co-reporter:Pengtao Ma, Rong Wan, Yanan Si, Feng Hu, Yueyan Wang, Jingyang Niu and Jingping Wang
Dalton Transactions 2015 - vol. 44(Issue 25) pp:NaN11523-11523
Publication Date(Web):2015/05/13
DOI:10.1039/C5DT01323B
Five members of a new family of polyoxometalate (POM)-ligated trinuclear lanthanoid (Ln) clusters with the general formula K20Li2[Ln3(μ3-OH)(H2O)8(AsW9O33)(AsW10O35(mal))]2·17H2O [Ln = Dy (1Dy), Tb (2Tb), Gd (3Gd), Eu (4Eu), and Sm (5Sm), mal = malate] have been synthesized, all of which consist of the dimeric {[Ln3(μ3-OH)(H2O)8(AsW9O33)[AsW10O35(mal)]}11− polyanion constructed from a {AsW9O33} and a {AsW10O35(mal)} building block linked by a tri-Ln cluster [Ln3(μ3-OH)(H2O)8]8+, where the two malate ligands play a key bridging role. The {AsW10O35(mal)} subunit can be viewed as the {AsW9O33} building block anchoring an additional tungsten center [WO2(mal)]. The electrospray ionization mass (ESI-MS) spectra indicate that the dimeric fragments of 1Dy and 2Tb are unstable, which are apt to produce the subunit [KH5Ln3(OH)(H2O)(AsW9O33)2]4− in solution. The solid-state photoluminescence measurements display the yellowish green emission for 1Dy and 5Sm, green emission for 2Tb and reddish orange emission for 4Eu, which are attributed to the LnIII f–f electron transitions. Magnetic property studies indicate that 1Dy displays probable SMM behaviour with slow magnetization relaxation, whereas the weak antiferromagnetic interactions exist in two {Ln3} clusters for 2Tb–5Sm.
Co-reporter:Shumin Chen, Ying Liu, Jipeng Guo, Pengzhen Li, Zhiyuan Huo, Pengtao Ma, Jingyang Niu and Jingping Wang
Dalton Transactions 2015 - vol. 44(Issue 22) pp:NaN10155-10155
Publication Date(Web):2015/05/07
DOI:10.1039/C5DT01046B
A multi-component polyoxometalate based on earth-abundant elements (NH4)10[Co8(H2O)10V10Mo23O104(OH)6]·34.5H2O (1) has been successfully obtained and characterized. Furthermore, compound 1 acted as a Lewis acid catalyst and promoted the conversion of carbon dioxide to a cyclic carbonate under mild reaction conditions.
Co-reporter:Xiaopeng Sun, Zhijie Liang, Pengtao Ma, Ran Ban, Mingshuang Jiang, Dongdi Zhang, Jingping Wang and Jingyang Niu
Dalton Transactions 2015 - vol. 44(Issue 40) pp:NaN17550-17550
Publication Date(Web):2015/09/08
DOI:10.1039/C5DT02471D
A novel organophosphonate-functionalized heteropolyoxomolybdate incorporated nickel cluster, CsNa9[H2{Ni3O2(H2O)6}(PMo6O21)2{Ni(OOCCH2NHCH2PO3)2}3]·21H2O (1), has been synthesized, which represents the first member of the family of oxomolybdenum organophosphonate containing hexa-nuclear Ni(II) in a polyanion framework. The polyanion comprises a unique ladder-type {Ni3O10(H2O)6} cluster and three {Ni(OOCCH2NHCH2PO3)2} bridgings, which are capped on either end by a {PMo6O28} group. Photocatalytic experiments indicate that 1 exhibits catalytic activity for the photodegradation of RhB solution. Furthermore, magnetic studies indicate that 1 displays antiferromagnetic interactions.
Co-reporter:Yuan Wang, Pengtao Ma and Jingyang Niu
Dalton Transactions 2015 - vol. 44(Issue 10) pp:NaN4682-4682
Publication Date(Web):2015/01/30
DOI:10.1039/C4DT02967D
A series of organic–inorganic hybrid rare earth complexes {[RE2(PO)2(H2O)10][H2Mo36O112(OH2)12(PO)4]}·5PO·2(CH3CN)·nH2O [n = 23–42, RE(III) = Nd(III), 1; Sm(III), 2; Eu(III), 3; Gd(III), 4; Dy(III), 5; Er(III), 6; Tm(III), 7; Yb(III), 8; Lu(III), 9; Y(III), 10; PO = piperidin-2-one] have been synthesized and fully characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, IR spectra, thermogravimetric analysis and UV-vis spectra. Structural analysis reveals that compounds 1–10 are isostructural and crystallize in the monoclinic P2(1)/n space group. Each compound contains a centrosymmetric anionic cluster [Mo36O112(OH2)12(PO)4]8−, which could be described as the derivative of [Mo36O112(OH2)16]8− with four water molecules substituted by organic PO molecules. Each {Mo18} subunit connects with one RE(III) ion via its two terminal O atoms from two independent {MoO6} octahedra. The eight coordinated RE(III) ion with a distorted tetragonal antiprism coordination geometry is also surrounded by another six oxygen atoms, five of them from five water molecules and the final one from one PO molecule. Compounds 1–10 show considerable photosensitive behavior under visible light excitation. In addition, compound 3 exhibits three emission bands at 580, 595 and 617 nm in the solid state, which could be assigned to 5D0→7F0, 5D0→7F1 and 5D0→7F2 transitions of Eu(III) ions, respectively.
Co-reporter:Yuan Wang, Xiaopeng Sun, Suzhi Li, Pengtao Ma, Jingping Wang and Jingyang Niu
Dalton Transactions 2015 - vol. 44(Issue 2) pp:NaN738-738
Publication Date(Web):2014/11/04
DOI:10.1039/C4DT01703J
Six tartrate-bridging rare-earth-substituted polytungstoarsenates [RE2(C4H4O6)(C4H2O6)(As W9O33)]218− (HoIII (1), ErIII (2), TmIII (3), YbIII (4), LuIII (5), and YIII (6)) have been synthesized under conventional solution conditions. They have been further characterized by elemental analyses, X-ray powder diffraction (XRPD), IR and UV-vis spectroscopy and single-crystal X-ray diffraction. Preliminary variable-temperature magnetic susceptibility measurements indicate that 1–4 exhibit antiferromagnetic coupling.
Co-reporter:Zhen Zhou, Dongdi Zhang, Lu Yang, Pengtao Ma, Yanan Si, Ulrich Kortz, Jingyang Niu and Jingping Wang
Chemical Communications 2013 - vol. 49(Issue 45) pp:NaN5191-5191
Publication Date(Web):2013/04/18
DOI:10.1039/C3CC41628C
The nona-CuII-containing tungstoarsenate(III) [H4{CuII9AsIII6O15(H2O)6}(α-AsIIIW9O33)2]8− (1a) has been synthesized and characterized. Polyanion 1a comprises a unique, cylindrical {CuII9AsIII6O15(H2O)6}6+ cluster, which forms a large central cavity and is capped on either end by an [α-AsIIIW9O33]9− capping group. It exhibits remarkable activity against K562 leukaemia cells, as well as induces HepG2 cell apoptosis and autophagy.
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]chloro(pyridine)-, (OC-6-42)-](http://img.cochemist.com/ccimg/23300/23295-32-1.png)
]chloro(pyridine)-, (OC-6-42)-](http://img.cochemist.com/ccimg/23300/23295-32-1_b.png)
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