Co-reporter:Xiuhua Wang, Yajie Liu, Mengtian Jin, Yuxing Wu, Lijuan Chen, and Jun-Wei Zhao
Crystal Growth & Design October 4, 2017 Volume 17(Issue 10) pp:5295-5295
Publication Date(Web):August 11, 2017
DOI:10.1021/acs.cgd.7b00823
Two series of novel organic–inorganic hybrid carboxylated rare-earth-substituted monolacunary Dawson-type phosphotungstate monomers [Hdap]4[RE(H2O)(Hpic)3][RE(Hpic)2 (α2-P2W17O61)]·21H2O [RE = GdIII (1), TbIII (2), DyIII (3), HoIII (4), ErIII (5), TmIII (6), YbIII (7), YIII (8); Hpic = 2-picolinic acid, dap = 1,2-diaminopropane] and dimers [H2dap]8[RE2(H2ox)2(ox)(α2-P2W17O61)2]·25H2O [RE = HoIII (9), ErIII (10), TmIII (11), YbIII (12), YIII (13); H2ox = oxalic acid] have been hydrothermally synthesized and characterized by elemental analyses, IR spectra, thermogravimetric measurements, and X-ray single-crystal diffraction. The monomeric polyoxoanion skeleton of isomorphic 1–8 is constructed from a monolacunary Dawson-type phosphotungstate implanted by a [RE1(Hpic)2]3+ cation in the polar position and supported by the other [RE2(H2O)(Hpic)3]3+ cation on the equatorial belt. Interestingly, two kinds of RE cations separately coordinate to two or three Hpic ligands in the form of N–C–C–O–RE containing five-membered ring fashion. The dimeric polyoxoanion backbone of isomorphic 9–13 is built by two mono-RE substituted Dawson-type phosphotungstate fragments [RE(H2ox)(α2-P2W17O61)]7– joined together by an ox2– linker. The visible photoluminescence spectra of solid-state 2, 3, 5, and 10 and the NIR photoluminescence properties for solid-state 5, 10, 7, and 12 at ambient temperature have been carried out, which are mainly derived from the RE3+ f–f electron transitions. Magnetic susceptibility measurements and fitting results of 3 demonstrate that 3 is a single-molecule magnet.
Co-reporter:Qing Han, Jian-Cai Liu, Yue Wen, Li-Juan Chen, Jun-Wei Zhao, and Guo-Yu Yang
Inorganic Chemistry June 19, 2017 Volume 56(Issue 12) pp:7257-7257
Publication Date(Web):June 5, 2017
DOI:10.1021/acs.inorgchem.7b00924
A family of unprecedented tellurotungstate-based organotin–rare-earth (RE) heterometallic hybrids [H2N(CH3)2]6H12Na2 {[Sn(CH3)W2O4(IN)][(B-α-TeW8O31)RE(H2O) (Ac)]2}2·25H2O [RE = CeIII (1), PrIII (2), NdIII (3), SmIII (4), EuIII (5), GdIII (6), TbIII (7); HIN = isonicotinic acid, HAc = acetic acid] were synthesized and characterized by elemental analyses, IR spectra, UV spectra, thermogravimetric analyses, powder X-ray diffraction, and single-crystal X-ray diffraction. The polyoxoanionic skeletons {[Sn(CH3)W2O4(IN)][(B-α-TeW8O31)RE(H2O) (Ac)]2}220– of 1–7 are constructed from two symmetrical units {[Sn(CH3)W2O4(IN)][(B-α-TeW8O31)RE(H2O) (Ac)]2}10– linked by two acetate connectors, which not only represent the first inorganic–organic hybrid RE-substituted tellurotungstates involving three different organic ligands, but also stand for the first samples of organotin–RE heterometallic polyoxometalate derivatives. The solid-state luminescent emission properties of 2–5 mainly display the characteristic emission bands of REIII cations, whereas during the emission procedure of 7, [B-α-TeW8O31]10– segments make a nonignorable contribution to the PL behavior of 7 accompanying by the occurrence of the intramolecular energy transfer from O→W LMCT energy to Tb3+ centers. Furthermore, 4@CTAB composites with peanutlike and honeycombed morphologies were prepared by a surfactant cetyltrimethylammonium bromide (CTAB). The time-resolved emission spectra of the 4@CTAB composite with CTAB/4 = 0.033/0.05 consolidate the energy transfer from CTAB to REIII centers. Variable-temperature magnetic susceptibility measurements for 2, 3, and 4 were performed.
Co-reporter:Yongsheng Zhu, Tao Hai, Xiaoxu Ji, Xu Chen, Shaobo Cui, Jinyang Zhu, Xiumei Xu, Junwei Zhao, Wen Xu
Journal of Luminescence 2017 Volume 181() pp:352-359
Publication Date(Web):January 2017
DOI:10.1016/j.jlumin.2016.09.037
Upconversion (UC) nanomaterials with the ability to convert incident infrared photons to visible or ultraviolet emissions have attracted remarkable interest and hold great promising applications ranging from bioimaging to display devices. However, their low UCL efficiency does not satisfy the requirement of various practical applications. In this work, we successfully prepared Dy2O3/Au and Sm2O3/Au nanocomposites by a simple co-precipitation method. X-Ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and photoluminescence (PL) spectroscopy were used to characterize the samples. The UC broadband enhancements illuminating with various power density of 980 nm are systemically investigated. The maximum UCL enhancement is 35-fold and 48-fold for Dy2O3/Au and Sm2O3/Au nanocomposites under 980 nm excitation. The UC population processes and enhancement mechanism are carefully studied. The luminescence enhancement in the composites is mainly attributed to the enhanced thermal effect.
Co-reporter:Jinglin Liu, Hailou Li, Rui Zheng, Yajie Liu, Guangfeng Jin, Lijuan Chen, Junwei Zhao
Journal of Solid State Chemistry 2017 Volume 256(Volume 256) pp:
Publication Date(Web):1 December 2017
DOI:10.1016/j.jssc.2017.09.015
•lanthanide-incorporated arsenotungstates.•duplicate {AsO2(OH)}-bridging lanthanide(Ln)-incorporated arsenotungstates.•the solid-state photoluminescence properties.Two {AsO2(OH)}-bridging lanthanide(Ln)-incorporated arsenotungstates (ATs) [H2N(CH3)2]8LnNa5 {[W3Ln2(H2O)8AsO8(OH)][B-α-AsW9O33]2}2·65H2O [Ln = ErIII (1), YbIII (2)] were synthesized by reaction of Na2WO4·2H2O, Ln(NO3)3·6H2O and NaAsO2 in the presence of dimethylamine hydrochloride. The common structural features of 1 and 2 are that the AsIII ions not only act as heteroatoms of the AT fragments but also function as the bridging groups to link two identical {[W3Ln2(H2O)8AsO8(OH)][B-α-AsW9O33]2} half-units. The results of TG analyses indicate that 1 and 2 undergo the similar three-step weight loss procedure between 25 and 800 °C. The first-step weight loss is attributable to the liberation of sixty-five lattice water molecules, the second-step weight loss corresponds to the release of sixteen coordination water molecules, ten protons as well as eight dimethylamine groups, and the third-step weight loss can be assigned to the sublimation of three As2O3 molecules. In addition, the solid-state photoluminescence properties of 1 and 2 have been investigated and mainly demonstrate the characteristic emission behaviors of ErIII ions and YbIII ions.Two {AsO2(OH)}-bridging lanthanide-incorporated arsenotungstates were synthesized and photoluminescence properties of the ErIII-containing species were intensively investigated.Download high-res image (464KB)Download full-size image
Co-reporter:Hai-Lou Li;Ya-Jie Liu;Jing-Lin Liu;Dr. Li-Juan Chen; Dr. Jun-Wei Zhao; Dr. Guo-Yu Yang
Chemistry - A European Journal 2017 Volume 23(Issue 11) pp:2673-2689
Publication Date(Web):2017/02/21
DOI:10.1002/chem.201605070
AbstractThree types of serine-decorated rare- earth-containing arsenotungstate [H2N(CH3)2]6NaH[RE2 W4O10(H2O)8(Ser)2(B-α-AsW9O33)2]⋅30 H2O (RE3+=Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, and Y3+; 1), [H2N(CH3)2]6Na6−xRExH4−2 x[RE4W8O19(H2O)10+y(OH)2(Ser)2(B-α-AsW9O33)4]⋅n H2O (RE3+=Tb3+, x=1, y=2, n=36; RE3+=Dy3+, Ho3+, Er3+, Yb3+, Y3+, x=0, y=0, n=38; RE3+= Tm3+, x=1, y=0, n=38; Ser=serine; 2), and [H2N(CH3)2]6−2 xNa2+3 xRExH10−6 x+y[RE4W8O19(H2O)8(OH)2(Ser)4(B-α-AsW9O33)4]⋅Cly⋅n H2O (RE3+=Ce3+, Pr3+, x=1, y=0, n=65; RE3+=Nd3+, Sm3+, x=0, y=0, n=65; RE3+=Eu3+, Gd3+, x=1, y=2, n=45; 3) were synthesized with the participation of the organic solubilizers dimethylamine hydrochloride and l-serine and were structurally characterized. The use of different amounts of rare-earth salts results in the structural transformation from dimerization to tetramerization of types 1–3. Type 1 is a dimeric sandwich-type assembly of a dual-Ser-participating [RE2W4O10(H2O)8(Ser)2]10+ entity sandwiched by two [B-α-AsW9O33]9− moieties, whereas types 2 and 3 have a tetrameric square structure formed by four [B-α-AsW9O33]9− moieties that anchor a dual/tetra- Ser-participating [RE4W8O19(H2O)10+y(OH)2(Ser)2]20+ or [RE4W8O19(H2O)8(OH)2(Ser)4]20+ core. The solid-state luminescence properties and lifetime–decay behaviors of these compounds were investigated. The chromaticity coordinates, dominant wavelengths, color purities, and correlated color temperatures were also calculated.
Co-reporter:Jiancai Liu;Jie Luo;Qing Han;Jing Cao;Lijuan Chen;You Song;Junwei Zhao
Journal of Materials Chemistry C 2017 vol. 5(Issue 8) pp:2043-2055
Publication Date(Web):2017/02/23
DOI:10.1039/C6TC05479J
A neoteric 1-D sinusoidal tungstoantimonate (TA) Na2H4{[Mn(H2O)3]3[Mn(H2O)2]2[Mn(H2O)][Mn(C2O4)]3[B-α-SbW9O33]2}·31H2O (1) was synthesized from the reaction of Na9[B-α-SbW9O33]·19.5H2O with MnCl2·4H2O with the assistance of oxalic acid and structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, powder X-ray diffraction and thermal analyses. In 1, an unprecedented oxalate-bridging nona-MnII {[Mn(H2O)3]3[Mn(H2O)2]2[Mn(H2O)][Mn(C2O4)]3}12+ cluster is clamped by two trivacant Keggin [B-α-SbW9O33]9− fragments forming a unique nona-MnII-encapsulated sandwich-type species. In the sandwich belt, the internal hexa-MnII {[Mn(H2O)2]2[Mn(H2O)][Mn(C2O4)]3}6+ ring is alternately concatenated with three [Mn(H2O)3]2+ ions situated at three vertices of an equicrural triangle through oxalate linkers, completing an approximately coplanar nona-MnII core. More interestingly, adjacent nona-MnII-sandwiched TA units are interconnected by double MnII–C2O4 linkages, giving rise to the first inorganic–organic hybrid 1-D chain high-nuclear Mn-sandwiched TA. Furthermore, the zero-field-cooling/field-cooled magnetization and alternating current magnetic susceptibility measurements reveal the occurrence of long-range ferromagnetic ordering and spin-glass behavior in 1, which are further consolidated by the fitting of the Arrhenius law and the conventional critical scaling law of spin dynamics.
Co-reporter:Peijun Gong;Yanyan Li;Cuiping Zhai;Jie Luo;Xuemeng Tian;Lijuan Chen;Junwei Zhao
CrystEngComm (1999-Present) 2017 vol. 19(Issue 5) pp:834-852
Publication Date(Web):2017/01/30
DOI:10.1039/C6CE02428A
Two classes of rare-earth-organic-containing Waugh-type manganomolybdates (NH4)8{[RE(Hina)(ina)(H2O)2][MnIVMo9O32]}2·12H2O [RE = La3+ (1), Pr3+ (2), Nd3+ (3)] and (NH4)3[RE(Hina)2(H2O)6][MnIVMo9O32]·7H2O [RE = Sm3+ (4), Eu3+ (5), Gd3+ (6), Tb3+ (7), Dy3+ (8), Ho3+ (9), Er3+ (10), Tm3+ (11), Yb3+ (12), Y3+ (13)] (Hina = isonicotinic acid) were prepared by means of a step-by-step synthetic strategy and further characterized by IR spectroscopy, elemental analyses, UV-visible spectroscopy and single-crystal X-ray diffraction. X-ray diffraction indicates that 1–3 consist of an organic–inorganic hybrid dimeric {[RE(Hina)(ina)(H2O)2][MnIVMo9O32]}28− core constituted by two [MnMo9O32]6− units linked via a dinuclear {[RE(Hina)(ina)(H2O)2]2}4+ cation whereas 4–13 are composed of an organic–inorganic hybrid [RE(Hina)2(H2O)6]3+ fragment and one [MnMo9O32]6− polyoxoanion. It should be pointed out that the nature of RE cations controls these two structure types. As far as we know, 1–13 represent the first examples of Waugh-type manganomolybdates including rare-earth-organic subunits so far. Furthermore, their photocatalytic activities for the degradation of azophloxine were probed in aqueous medium and 3 and 8 as representatives were systematically investigated involving the influence of the optimal pH, catalyst dosage and the doping amount of VK-TA18 nanometer titanium dioxide on the photocatalytic activities. The solid-state photoluminescence properties and lifetime decay behaviors of 3, 4 and 5 in UV-visible or near-infrared regions were also examined at ambient temperature.
Co-reporter:Hailou Li, Yajie Liu, Rui Zheng, Xing Ma, Lijuan Chen, Junwei Zhao
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2017 Volume 176(Volume 176) pp:
Publication Date(Web):5 April 2017
DOI:10.1016/j.saa.2017.01.016
•Rare-earth containing docosatungstates•The hendecatungstate [W11O38H]9 − subunit•Solid-state luminescence propertiesThree rare-earth containing docosatungstates Na3H2[RE(H2O)4][RE(H2O)5]2[W22O74H2]·36H2O [RE = DyIII (1), HoIII (2), YIII (3)] have been synthesized by reaction of Na2WO4·2H2O, dimethylamine hydrochloride (DMAHC) and RE(NO3)3·6H2O in the aqueous solution and characterized by elemental analyses, IR spectra, thermogravimetric (TG) analysis, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. 1–3 are isomorphous and each molecular unit consists of a S-shaped docosatungstate [W22O74H2]14 − polyoxoanion with two supporting [RE(H2O)5]3 + cations and one disordered [RE(H2O)4]3 + cation. The [W22O74H2]14 − polyoxoanion can be viewed as combination of two hendecatungstate [W11O38H]9 − subunits in the staggered fashion by sharing two μ2-O atoms. The TG curves of 1–3 reveal the one-step weight loss between 25 °C to 700 °C. Moreover, both 1 and 2 demonstrate the characteristic luminescence emission behaviors of the corresponding RE3 + ions and their lifetime decay curves can be well fitted to the double exponential function. In addition, the CIE chromaticity coordinates of 1 and 2 have been obtained based on their corresponding emission spectra, and their dominant wavelengths and color purities have been also calculated.Three rare-earth containing docosatungstates Na3H2[RE(H2O)4][Ln(H2O)5]2[W22O74H2]·36H2O [Ln = DyIII, HoIII, YIII] were synthesized and their photoluminescence properties were investigated.Download high-res image (109KB)Download full-size image
Co-reporter:Peijun Gong, Guangfeng Jin, Changtong Lu, Lijuan Chen, Junwei Zhao
Inorganic Chemistry Communications 2017 Volume 83(Volume 83) pp:
Publication Date(Web):1 September 2017
DOI:10.1016/j.inoche.2017.05.027
•Rare-earth-containing polyoxometalate•Lanthanide-containing Keggin silicomolybdate•Isonicotinic acid•Electrochemical propertiesTwo rare-earth–isonicotinic-acid containing silicomolybdates [NH4]6[RE(INA)2(HINA)(H2O)3]2[α-SiMo12O40]2·6H2O [RE = NdIII (1), ErIII (2); HINA = isonicotinic acid] have been synthesized in the conventional aqueous solution and characterized by elemental analyses, IR spectra, UV spectra and single-crystal X-ray diffraction. Both 1 and 2 crystallize in the triclinic P–1 space group and consist of two typical Keggin [α-SiMo12O40]4 − polyanions, one isolated rare-earth-isonicotinic-acid [RE(INA)2(HINA)(H2O)3]22 + dimeric complex cation, six NH4+ ions and six lattice water molecules. Interestingly, two rare-earth ions are linked by four INA− ligands in the [Ln(INA)2(HINA)(H2O)3]22 + complex cation, which is very rare in polyoxometalate chemistry. The UV spectral measurements of 1 indicate that 1 is stable in aqueous solution in the pH range of 4.49–9.39. Furthermore, the electrochemical and electrocatalytic properties of 1 have been measured by cyclic voltammetry in 0.5 mol·L− 1 Na2SO4 + H2SO4 aqueous solution at the scan rate of 100 mV·s− 1.Two rare-earth–isonicotinic-acid containing silicomolybdates have been synthesized and characterized.Download high-res image (282KB)Download full-size image
Co-reporter:Jun-Wei Zhao, Yan-Zhou Li, Li-Juan Chen and Guo-Yu Yang
Chemical Communications 2016 vol. 52(Issue 24) pp:4418-4445
Publication Date(Web):05 Feb 2016
DOI:10.1039/C5CC10447E
With the rapid development of science and technology and the trend of multidisciplinary pervasion, POM-based TM–RE heterometallic chemistry (POM = polyoxometalate, TM = transition-metal, RE = rare-earth) has become one of the most rapidly growing and challengeable areas of inorganic chemistry due to the impressive structural diversities, various chemical compositions and potential applications of these materials in magnetism, optics, electrochemistry, electrocatalysis and materials science. Over the past several years, continuous interest and persisting efforts have been dedicated to the preparation and exploration of POM-based TM–RE heterometallic derived materials (PTRHDMs), which have led to more than two hundred PTRHDMs. In this review, we summarize the structural types of reported PTRHDMs together with synthetic strategies, structural motifs and relevant functional applications. The exciting array of this emerging research theme presages continuous growth and great vitality. In the last section, some prospects of this branch are also presented and possible guidance for future work is outlined.
Co-reporter:Lei-Lei Li, Gao-Juan Cao, Jun-Wei Zhao, Huan He, Bai-Feng Yang, and Guo-Yu Yang
Inorganic Chemistry 2016 Volume 55(Issue 11) pp:5671
Publication Date(Web):May 24, 2016
DOI:10.1021/acs.inorgchem.6b00754
Under hydrothermal conditions, six series of novel lanthanide (Ln) organogermanates (LnGs) [Ln8Ge12(μ3-O)24E12(H2O)16]·14H2O (Ln3+ = Pr3+, 1; Nd3+, 2; Sm3+, 3; Eu3+, 4; Gd3+, 5; one-dimensional (1-D) LnG cluster organic chain (LnGCOC)), {[Nd8Ge12(μ3-O)24E12(H2O)10](μ2-H2O)2[Nd8Ge12(μ3-O)24E12(H2O)16]}·18H2O (6, two-dimensional (2-D) planar LnG cluster organic layer (LnGCOL)), {[Ln2GeE(HO)2O(H2O)(CH3COO)2(CO3)]2[Ln8Ge12E12(μ3-O)24(H2O)10]}·6H2O (Ln3+ = Pr3+, 7; Nd3+, 8; 2-D wave-shaped LnGCOL), [TbGeE(HO)2O(H2O)(pca)]2[Tb8Ge12E12(μ3-O)24(H2O)8]·10H2O (9, three-dimensional (3-D) LnG cluster organic framework (LnGCOF)), {([Nd(pza)2(H2O)2]2[Nd8Ge12E12(μ3-O)24(H2O)12])([Nd(pza)2]2[Nd8Ge12E12(Hpza)2(μ3-O)24(H2O)10])}·4OH·14H2O (10, 3-D LnGCOF), {[Nd8Ge12E12(μ3-O)24(H2O)10][Nd(pca)(pda)(H2O)]2}·12H2O (11, 3-D LnGCOF) and {[Nd8Ge12E12(μ3-O)24(H2O)10][Nd(pza)(pda)(H2O)]2}·12H2O (12, 3-D LnGCOF) (Hpca = 2-picolinic acid, H2pda = 2,6-pyridinedicarboxylic acid, Hpza = 2-pyrazinecarboxylic acid) were prepared by introducing the second auxiliary ligands into the organogermanate–lanthanide–oxide reaction system. The obtainment of these LnGs realized the utilization of the second auxiliary ligands inducing the assembly from 1-D LnGCOCs to 2-D LnGCOLs and 3-D LnGCOFs based on LnG cluster (LnGC) {Ln8Ge12E12(μ3-O)24(H2O)16}({Ln8Ge12}) units and Ln–organic complexes or organic ligand connectors. It should be noted that the well-organized structural constructions of 1–12 can be visualized as the gradual replacement of active water sites located at equatorial and polar positions on the hypothetical [Ln8Ge12(μ3-O)24E12(H2O)18] LnGC core with oxygen or nitrogen atoms from organic ligands. The solid-state luminescent properties of 2, 3, 4, 6, and 8–12 have been investigated at room temperature.
Co-reporter:Hailou Li, Yajie Liu, Rui Zheng, Lijuan Chen, Jun-Wei Zhao, and Guo-Yu Yang
Inorganic Chemistry 2016 Volume 55(Issue 8) pp:3881-3893
Publication Date(Web):April 5, 2016
DOI:10.1021/acs.inorgchem.6b00061
The one-pot assembly reaction of Na2WO4·2H2O, RE(NO3)3·6H2O, and NaAsO2 in the participation of dimethylamine hydrochloride as an organic solubilizing agent in the acidic aqueous solution led to a class of trigonal pyramidal {AsO2(OH)} bridging rare-earth substituted arsenotungstate (AT) aggregates [H2N(CH3)2]8Na8{[W3RE2(H2O)8AsO8(OH)][B-α-AsW9O33]2}2·65H2O [RE = EuIII (1), GdIII (2), TbIII (3), DyIII (4), HoIII (5), YIII (6)], which were structurally characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, and thermogravimetric (TG) analyses. The common structural feature of 1–6 is that their polyoxoanions consist of a novel tetrameric unit [(W3RE2(H2O)8AsO8(OH))(B-α-AsW9O33)2]216– constituted by four trivacant Keggin [α-AsW9O33]9– fragments linked through an unseen elliptical [W6RE4(H2O)16As2O16(OH)2]20+ moiety. Their polyoxoanionic infrastructures can also be described as a fusion of two equivalent dimeric subunits [(W3RE2(H2O)8O7)(B-α-AsW9O33)2]8– bridged via two μ2-{AsO2(OH)} linkers. To the best of our knowledge, such a linking mode with trigonal pyramidal {AsO2(OH)} groups as linkers connecting adjacent RE containing polyoxometalate moieties together is very rare. The thermal stability of 1–6 was also investigated on the crystalline samples, and the thermal decomposition processes of 1, 4, and 6 were comparatively deeply studied. The fluorescent properties and decay times of 1, 3, and 4 were measured, and they exhibit the characteristic emissions of RE centers. The lifetimes of 1 and 3 mainly originate from the contribution of RE ions whereas the overall lifetime of 4 is contributed by the synergistic interactions of AT fragments and Dy3+ ions.
Co-reporter:Xing Ma, Hailou Li, Lijuan Chen and Junwei Zhao
Dalton Transactions 2016 vol. 45(Issue 12) pp:4935-4960
Publication Date(Web):09 Feb 2016
DOI:10.1039/C5DT05020K
Currently, transition-metal substituted polyoxotungstates (TMSPTs) have developed as a fast growing and challengeable subfamily of polyoxoxmetalates (POMs). Before 2005, the number of TM cores in TMSPTs was mostly lower than five. Since 2005, numerous inorganic or organic–inorganic TMSPTs with more than five TM cores (denoted as high-nuclear TMSPTs) have continuously been excavated and investigated. In this perspective, we endeavor to discuss the synthetic methodologies, structural diversities and relevant properties of the high-nuclear TMSPTs reported in the past decade. Future perspectives and opportunities on TMSPTs are included in the last section. This review is meant to provide fodder and guidance for further exploration and discovery of more high-nuclear TMSPTs with innovative architectures and remarkable functionality.
Co-reporter:Jiancai Liu, Qing Han, Lijuan Chen and Junwei Zhao
CrystEngComm 2016 vol. 18(Issue 6) pp:842-862
Publication Date(Web):04 Jan 2016
DOI:10.1039/C5CE02378E
Heterometallic polyoxotungstates (HMPOTs) are still a challenging and attractive materials in polyoxometalate chemistry despite having generated remarkable interest in recent years not only on account of a variety of new structures and topologies but also because of their multiple potential applications in catalysis, magnetism, nanoscience, electrochemistry and photochemistry. This brief highlight article is principally focused on an overview of four types of HMPOTs: polyoxotungstate-based main-group (MG) and transition-metal (TM) heterometallic derivatives (PMGTMHDs), polyoxotungstate-based TM and TM heterometallic derivatives (PTMTMHDs), polyoxotungstate-based rare-earth (RE) and TM heterometallic derivatives (PRETMHDs) and polyoxotungstate-based RE and RE heterometallic derivatives (PREREHDs), and gives a summary of some representative examples involving their syntheses, structures and related properties. In addition, an outlook on these materials is also provided.
Co-reporter:Hailou Li, Wen Yang, Xiuhua Wang, Lijuan Chen, Jianru Ma, Liwei Zheng, and Junwei Zhao
Crystal Growth & Design 2016 Volume 16(Issue 1) pp:108-120
Publication Date(Web):November 24, 2015
DOI:10.1021/acs.cgd.5b00996
Three types of new lanthanoid(Ln)-containing isopolyoxotungstates [H2N(CH3)2]6Na6[Ln4(H2O)22W28O94H2]2·113H2O [Ln = Pr3+ (1), Nd3+ (2), Sm3+ (3)], Na2[Eu(H2O)7]2[Eu(H2O)5]2[W22O74H2]·20H2O (4), and Na3H2[Ln(H2O)4][Ln (H2O)5]2[W22O74H2]·36H2O [Ln = Gd3+ (5), Tb3+ (6), Er3+ (7), Tm3+ (8), Yb3+ (9), Lu3+ (10)] have been obtained by reacting Na2WO4·2H2O with Ln(NO3)3·6H2O in the presence of dimethylamine hydrochloride in the acidic aqueous solution and structurally characterized by elemental analyses, IR spectroscopy, UV spectroscopy, electrospray ionization mass spectrometry (ESI–MS), thermogravimetric (TG) analyses, and single-crystal X-ray diffraction. 1, 2, and 3 are isostructural and display a one-dimensional (1-D) chain-like alignment built by hexameric Ln8-comprising [Ln4(H2O)22W28O94H2]212– entities via [Ln(H2O)5]3+ connectors. The [Ln4(H2O)22W28O94H2]212– entity consists of two [Ln4(H2O)22W28O94H2]6– subunits connected by two W–O–Ln–O–W linkers. Intriguingly, the rare λ-shaped octacosatungstate [W28O94H2]18– moiety observed in the [Ln4(H2O)22W28O94H2]6– subunit is composed of two undecatungstate [W11O38H]9– fragments joined through a hexatungstate [W6O22]8– fragment by sharing four μ2-O atoms. In 4, 22-isopolytungstate [W22O74H2]14– anions are interlinked together by four W–O–Eu1–O–W linkers giving rise to the 1-D chain motif, and then adjacent 1-D chains are further bridged through multiple W–O–Eu2–O–W connectors to engender the two-dimensional extended sheet structure with the 4-connected topology. The isomorphic 5–10 demonstrate the discrete structure consisting of a [Ln(H2O)4][Ln (H2O)5]2[W22O74H2]8– unit. The pH ranges in which 3, 4, and 9 are stable in aqueous solution have been examined by virtue of UV and ESI–MS spectra. The solid-state luminescent properties of 3, 4, and 6 have been probed at room temperature. 3 displays the pink emission derived from characteristic emission bands of the Sm3+ cations that correspond to transitions from the 4G5/2 excited-state to lower 6HJ (J = 5/2, 7/2, 9/2, 11/2) levels, 4 emits the red light that mainly results from the 5D0 → 7F2 transition of the Eu3+ cations, and 6 manifests the green luminescence mainly originating from the 5D4 → 7F5 transition of the Tb3+ cations. Their lifetime decay curves all conform to the single exponential function, affording their lifetimes of 8094.19 ns, 149.00 μs and 384.89 μs, respectively.
Co-reporter:Lei-Lei Li, Rui Pan, Jun-Wei Zhao, Bai-Feng Yang and Guo-Yu Yang
Dalton Transactions 2016 vol. 45(Issue 30) pp:11958-11967
Publication Date(Web):25 May 2016
DOI:10.1039/C6DT01629D
Six new lanthanide (Ln) germanate cluster organic frameworks (LnGeCOFs) derived from {Ln8Ge12} cage cluster units {[Nd(pza)2(H2O)] [Nd8Ge12(μ3-O)24E12(pza)(H2O)12]}·3H2O (1), {[Dy(CH3COO)(CO3)(H2O)]2[Dy8Ge12(μ3-O)24E12(H2O)12]}·11H2O (2), {[TbGeE(HO)2O(pza) (H2O)]2[Tb8Ge12(μ3-O)24E12(H2O)6]}·18H2O (3), {[DyGeE(HO)2O(C3H5NO2)(H2O)]2[Dy8Ge12(μ3-O)24E12(H2O)8]}·8H2O (4), {[Tb(pca)2 (H2O)]3[Tb8Ge12(μ3-O)24E12(H2O)4]}·(OH)3·10H2O (5) and {[Dy(pza)2(H2O)][Dy(pza)2(H2O)2][Dy(pza)3(H2O)][Dy8Ge12(μ3-O)24E12(pza)(HCOO) (H2O)6]}·5H2O (6) have been hydrothermally synthesized and structurally characterized. Increasing the amount of the second ligands can induce not only the assembly from 1 to 5, 6 based on Ln oxides as the starting sources, but also the assembly from 2 to 3, 4 based on Ln salts as the starting sources. The successful preparation of these LnGeCOFs suggests the importance of the second ligands in the structural construction of 1–6. To our knowledge, 1 is the first example that includes right- and left-handed helical chains among LnGeCOFs based on bis(carboxyethylgermanium)sesquioxide. 2, 4 and 6 are the first dysprosium incorporated organogermanates based on bis(carboxyethylgermanium)sesquioxide. 4 and 5 display very open framework structures with a solvent-accessible volume of 34.6% for 4 and 35.0% for 5. Moreover, the solid-state photoluminescence properties of 1, 3 and 5 have been investigated at room temperature and they exhibit the characteristic emission bands derived from Ln cations.
Co-reporter:Longhui Sun, Yajie Liu, Xiuhua Wang, Hailou Li, Jie Luo, Lijuan Chen, Junwei Zhao
Synthetic Metals 2016 Volume 217() pp:256-265
Publication Date(Web):July 2016
DOI:10.1016/j.synthmet.2016.04.008
•Polyoxometalate-based copper–lanthanide heterometallic derivatives.•Inorganic–organic hybrid copper–lanthanide heterometal comprising germanotungstates.•The photoluminescence properties of the Eu3+ ions.The hydrothermal reaction of K8Na2[A-α-GeW9O34]·25H2O, Cu(CH3COO)2·H2O, Ln(NO3)·6H2O and ethylenediamine (en) has led to a series of inorganic–organic hybrid copper–lanthanide heterometal comprising germanotungstates (GTs) [Cu(en)2(H2O)]6[Ln(H2O)(CH3COO)(α-GeW11O39)]2·8H2O [Ln = Nd3+ (1), Sm3+ (2), Eu3+ (3), Gd3+ (4), Dy3+ (5), Ho3+ (6)], which have been characterized by elemental analyses, IR spectra, thermogravimetric (TG) analyses and single-crystal X-ray diffraction. Their common feature of 1–6 is that they all comprise a CH3COO-bridging mono-Ln substituted dimeric GT fragment [Ln(H2O)(CH3COO)(α-GeW11O39)]212− with six supporting [Cu(en)2(H2O)]2+ complex cations. To the best of our knowledge, such monovacant Keggin-type GTs containing both Cu–Ln heterometal centers and mixed en and acetate ligands are very rare. The luminescence properties and the lifetime decay behavior of the solid sample of 3 have been intensively investigated at room temperature.A series of inorganic–organic hybrid copper–lanthanide heterometal comprising germanotungstates were synthesized. Photoluminescence properties of the Eu-containing species were intensively investigated.
Co-reporter:Yanyan Li, Yajie Liu, Peijun Gong, Xuemeng Tian, Jie Luo, Junwei Zhao
Inorganic Chemistry Communications 2016 Volume 74() pp:42-47
Publication Date(Web):December 2016
DOI:10.1016/j.inoche.2016.10.036
•Organic–inorganic hybrid polyoxometalate-based materials•Isonicotinate-bridging lanthanide substituted Keggin-type phosphotungstates•Solid-state visible and near-infrared fluorescence properties and lifetime decay behaviorsTwo organic–inorganic hybrid isonicotinate-bridging lanthanide substituted phosphotungstates [H2N(CH3)2]8[Ln(H2O) (INA)(α-HPW11O39)]2·14H2O (Ln = HoШ for 1, ErШ for 2) (HINA = isonicotinic acid) have been obtained by reaction of the Na9[α-PW9O34]·16H2O precursor, Ln(NO3)3·6H2O, C2H7N·HCl and HINA in aqueous solution and structurally characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction and thermogravimetric analysis. Isostructural 1 and 2 consist of one inorganic–organic hybrid dimeric {[Ln(H2O)(INA)(α-HPW11O39)]2}8 − core constituted by two symmetrically mono-Ln substituted Keggin subunits [Ln(H2O)(INA)(α-HPW11O39)]4 − bridged by two INA− ligands in the (η2,μ-1,1) fashion. Intriguingly, adjacent hybrid dimeric {[Ln(H2O)(INA)(α-HPW11O39)]2}8 − cores can be extended into a 2-D supramolecular layer via hydrogen bonding interactions. To our knowledge, 1 and 2 represent the first isonicotinate-bridging dimeric mono-lanthanide substituted phosphotungstates. Furthermore, the solid-state fluorescence properties and lifetime decay behaviors of 1 and 2 in visible and near-infrared regions have also been investigated in detail.Two organic–inorganic hybrid isonicotinate-bridging lanthanide substituted phosphotungstates were successfully synthesized and their solid-state fluorescence properties were also investigated.
Co-reporter:Xiuhua Wang, Qing Han, Lijuan Chen, Junwei Zhao
Inorganic Chemistry Communications 2016 Volume 63() pp:24-29
Publication Date(Web):January 2016
DOI:10.1016/j.inoche.2015.11.008
•1-D and 2-D inorganic–organic hybrid polyoxomolybdates•Organic–inorganic hybrid octamolybdates•The photocatalytic degradation towards rhodamine-BTwo new 1-D and 2-D inorganic–organic hybrid polyoxomolybdates [H2dap]2[x-Mo8O26]·2H2O (1) and [Cu(dap)2]2[β-Mo8O26] (2) (dap = 1,2-propanediamine) have been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectra, powder X-ray diffraction and single-crystal X-ray diffraction. The most remarkable structural differences between them are that 1 displays a 1-D chain constructed from [x-Mo8O26]4 − clusters through two terminal O atoms from adjacent [x-Mo8O26]4 − clusters whereas 2 demonstrates the 2-D extended layer made up of [β-Mo8O26]4 − clusters via [Cu(dap)2]2 + connectors. To our knowledge, the [x-Mo8O26]4 − cluster in 1 is reported for the first time. The thermogravimetric (TG) curve of 1 shows a two-step weight loss whereas the TG decomposition of 2 only proceeds in one stage. Additionally, their electrochemical behaviors and their photocatalytic degradation properties towards rhodamine-B are also investigated.Two 1-D and 2-D inorganic–organic hybrid polyoxomolybdates [H2dap]2[x-Mo8O26]·2H2O (1) and [Cu(dap)2]2[β-Mo8O26] (2) (dap = 1,2-propanediamine) have been hydrothermally synthesized and structurally characterized.
Co-reporter:Peijun Gong, Yanyan Li, Jie Luo, Lijuan Chen, Junwei Zhao
Inorganic Chemistry Communications 2016 Volume 71() pp:113-118
Publication Date(Web):September 2016
DOI:10.1016/j.inoche.2016.07.014
•Inorganic–organic hybrids with mixed organic components•Copper-2-picolinic-acid germanomolybdates•1,3-bis[tris(hydroxymethyl)methylamino]propane•Electrochemical propertiesTwo inorganic–organic hybrids based on saturated α-Keggin-type germanomolybdates with mixed organic components [H2DAP]2[Cu(PA)2][α-GeMo12O40]·8H2O (1) and [NH4]2[H8L] [Cu(PA)2][α-GeMo12O40]·8H2O (2) (DAP = 1.2-diaminopropane, HPA = 2-picolinic acid, H6L = 1,3-bis[tris(hydroxymethyl)methylamino]propane) have been obtained via the conventional aqueous solution method and structurally characterized by elemental analysis, IR spectra, thermogravimetric (TG) analysis and single-crystal X-ray diffraction. 1 stands for an one-dimensional linear organic–inorganic hybrid germanomolybdate chain constructed from classical Keggin [α-GeMo12O40]4 − units supported by [Cu(PA)2] linkers, whereas 2 represents the first hybrid germanomolybdate containing the H6L component and consists of a saturated α-Keggin polyanion [α-GeMo12O40]4 −, a diprotonated [H8L]2 + cation, a copper coordination complex [Cu(PA)2], two ammonium cations [NH4]+ and eight lattice water molecules. Furthermore, the electrochemical and electrocatalytic properties of 1 and 2 have also been investigated in detail.Two inorganic–organic hybrids based on saturated α-Keggin-type germanomolybdates with mixed organic components have been synthesized and their electrochemical properties have been probed.
Co-reporter:Qing Han, Yue Wen, Jiancai Liu, Lijuan Chen, Junwei Zhao
Inorganic Chemistry Communications 2016 Volume 71() pp:54-60
Publication Date(Web):September 2016
DOI:10.1016/j.inoche.2016.07.002
•Inorganic–organic hybrid CuIICeIII heterometallic germanotungstate•1-D CuIICeIII heterometallic chain architecture•Solid-state electrochemical and electrocatalytic propertiesA new 1:2-type inorganic–organic hybrid CuIICeIII heterometallic germanotungstate (GT) derivative KNa2H9[enH2]2 [Cu(en)2(H2O)]2[Cu(en)2]2{Cu(en)2[Ce(α-GeW11O39)2]2}·14H2O (1) (en = ethylenediamine) was obtained by simultaneously introducing Cu2 + and Ce4 + cations to the trivacant Keggin-type [A-α-GeW9O34]10 − system in the help of extra Na2WO4·2H2O and en ligand under hydrothermal conditions and was further characterized by elemental analyses, IR spectrum, thermogravimetric (TG) analysis and single-crystal X-ray diffraction. 1 exhibits a 1-D CuIICeIII heterometallic chain architecture by tetrameric {Cu(en)2[Ce(α-GeW11O39)2]2}24 − units via K+ cations. Moreover, its solid-state electrochemical and electrocatalytic properties have been measured in 0.5 mol L− 1 Na2SO4 + H2SO4 aqueous solution by entrapping them in a carbon paste electrode, indicating that 1 displays apparent electrocatalytic activities for nitrite, bromate and hydrogen peroxide reduction.A 1:2-type inorganic–organic hybrid CuIICeIII heterometallic germanotungstate derivative has been synthesized and the electrochemical properties of 1 have been studied.
Co-reporter:Hailou Li, Shenzhen Chang, Xing Ma, Jinglin Liu, Jie Luo, Junwei Zhao
Inorganic Chemistry Communications 2016 Volume 72() pp:45-49
Publication Date(Web):October 2016
DOI:10.1016/j.inoche.2016.08.003
•1-D Krebs-type heteropolyoxotungstates prepared by the one-pot self-assembly reaction of simple materials•1-D chain structure constructed from Krebs-type [X2W21NaO72(OH)2]13 − fragments linked by sharing four W–O–W connectors•Electrochemical properties of heteropolyoxotungstates in Na2SO4 + H2SO4 aqueous solutionBy the one-pot self-assembly reaction of simple materials under acidic aqueous solution, two 1-D chain Krebs-type heteropolyoxometalates [H2N(CH3)2]2Na11[X2W21NaO72(OH)2]·34H2O (X = SbIII for 1, BiIII for 2) have been successfully synthesized and structurally characterized by elemental analysis, IR spectra, UV spectra, thermogravimetric (TG) analysis and X-ray single-crystal diffraction. The most prominent structural feature of 1 and 2 is that both display an interesting 1-D chain alignment constructed from Krebs-type [X2W21NaO72(OH)2]13 − fragments connected by sharing four W–O–W connectors, which is for the first time observed in the polyoxometalate chemistry. Additionally, the electrochemical properties of 1 and 2 have been studied in 0.5 mol L− 1 Na2SO4 + H2SO4 supporting electrolyte.Two 1-D Krebs-type heteropolyoxometalates constructed from Krebs-type [X2W21NaO72(OH)2]13 − fragments connected by four W–O–W connectors were synthesized and characterized.
Co-reporter:Han Xue;Dr. Jun-Wei Zhao;Rui Pan; Bai-Feng Yang;Dr. Guo-Yu Yang;Dr. Hong-Sheng Liu
Chemistry - A European Journal 2016 Volume 22( Issue 35) pp:12322-12331
Publication Date(Web):
DOI:10.1002/chem.201600622
Abstract
Under hydrothermal conditions, replacement of the water molecules in the [MnIII4MnII2O4(H2O)4]8+ cluster of mixed-valent Mn6 sandwiched silicotungstate [(B-α-SiW9O34)2MnIII4MnII2O4(H2O)4]12− (1 a) with organic N ligands led to the isolation of five organic–inorganic hybrid, Mn6-substituted polyoxometalates (POMs) 2–6. They were all structurally characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, diffuse-reflectance spectroscopy, and powder and single-crystal X-ray diffraction. Compounds 2–6 represent the first series of mixed-valent {MnIII4MnII2O4(H2O)4−n(L)n} sandwiched POMs covalently functionalized by organic ligands. The preparation of 1–6 not only indicates that the double-cubane {MnIII4MnII2O4(H2O)4−n(L)n} clusters are very stable fragments in both conventional aqueous solution and hydrothermal systems and that organic functionalization of the [MnIII4MnII2O4(H2O)4]8+ cluster by substitution reactions is feasible, but also demonstrates that hydrothermal environments can promote and facilitate the occurrence of this substitution reaction. This work confirms that hydrothermal synthesis is effective for making novel mixed-valent POMs substituted with transition-metal (TM) clusters by combining lacunary Keggin precursors with TM cations and tunable organic ligands. Furthermore, magnetic measurements reveal that 3 and 6 exhibit single-molecule magnet behavior.
Co-reporter:Han Xue;Dr. Jun-Wei Zhao;Rui Pan; Bai-Feng Yang;Dr. Guo-Yu Yang;Dr. Hong-Sheng Liu
Chemistry - A European Journal 2016 Volume 22( Issue 35) pp:
Publication Date(Web):
DOI:10.1002/chem.201683562
Co-reporter:Lijuan Chen, Fang Zhang, Xing Ma, Jie Luo and Junwei Zhao
Dalton Transactions 2015 vol. 44(Issue 28) pp:12598-12612
Publication Date(Web):28 May 2015
DOI:10.1039/C5DT00696A
Two classes of novel tetra-iron substituted sandwich-type arsenotungastates (ATs) with supporting lanthanide (Ln) pendants KNa2 [Ln(H2O)7][Fe4(H2O)10(B-β-AsW9O33)2]·21H2O [Ln = LaIII (1), PrIII (2), NdIII (3), SmIII (4)] and [Ln(H2O)8]2[Fe4(H2O)8(L-thr)2(B-β-AsW9O33)2]·20H2O [Ln = LaIII (5), PrIII (6), NdIII (7), SmIII (8), EuIII (9), GdIII (10), TbIII (11), DyIII (12), ErIII (13)] (L-thr = L-threonine) have been synthesized by the hydrothermal reaction of the [As2W19O67(H2O)]14− precursor with Fe3+ cations and Ln3+ cations in the presence of L-thr or L-leucine and L-alanine, and further characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. Structural analyses indicate that 1–4 display the inorganic 2-D sheet architecture constructed from tetra-iron sandwiched AT [Fe4(H2O)10(B-β-AsW9O33)2]6− fragments by bridging [Ln(H2O)7]3+ cations whereas the molecular structures of the isostructural 5–13 consist of an organic–inorganic hybrid tetra-iron substituted sandwich-type AT [Fe4(H2O)8(L-thr)2(B-β-AsW9O33)2]6− fragment and two pendant [Ln(H2O)8]3+ cations. As far as we know, 1–4 represent the rare inorganic 2-D extended ATs based on transition-metal substituted sandwich-type polyoxometalate units and Ln linkers and 5–13 are the first Fe–Ln heterometallic ATs with amino acid ligands. The solid state photoluminescence (PL) measurements of 9 and 11 have been performed at room temperature. The PL emission of 9 is mainly derived from the characteristic 5D0 → 7F2 (J = 4–0) transitions of the EuIII cations whereas the PL behavior of 11 stems from the common contribution of the 5D4 → 7FJ (J = 5–3) transitions of the TbIII ions and oxygen-to-metal (O → W) charge-transfer transitions of AT segments. The thermogravimetric (TG) analyses of 1–4 and 6–12 have been investigated.
Co-reporter:Xing Ma, Wen Yang, Lijuan Chen and Junwei Zhao
CrystEngComm 2015 vol. 17(Issue 43) pp:8175-8197
Publication Date(Web):14 Sep 2015
DOI:10.1039/C5CE01240F
Owing to their unique and abundant structures and potential multi-fold applications in various fields such as luminescence, magnetism, catalysis, etc., rare-earth-containing polyoxometalates (RECPs) play an important role in the development of polyoxometalate chemistry. In this article, the major progress in RECPs made in the past decade involving synthetic strategies, structural characteristics and some significant properties related to optics, catalysis and magnetism is highlighted and discussed. The final section is committed to looking forward to some future perspectives in this field and providing some personal insights or viewpoints for the ongoing trends in the future.
Co-reporter:Lijuan Chen, Jing Cao, Xinghua Li, Xing Ma, Jie Luo and Junwei Zhao
CrystEngComm 2015 vol. 17(Issue 27) pp:5002-5013
Publication Date(Web):20 May 2015
DOI:10.1039/C5CE00633C
The rational self-assembly of a trilacunary Keggin precursor with Fe3+ and RE3+ (rare-earth) ions via a conventional aqueous solution method has led to a series of novel tungstoantimonate-based Fe–RE heterometallic derivatives [Pr(H2O)8][Pr(H2O)6][Fe4(H2O)10(B-β-SbW9O33)2]·16H2O (1) and [RE(H2O)7]2[Fe4(H2O)10(B-β-SbW9O33)2]·22H2O [RE = TbIII (2), DyIII (3), LuIII (4), YIII (5)], which have been further structurally characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction (PXRD), single-crystal X-ray diffraction and thermogravimetric (TG) analysis. To the best of our knowledge, 1–5 represent the first purely inorganic Fe–RE heterometallic tungstoantimonates based on the trilacunary Keggin [B-β-SbW9O33]9− unit. In 1, the tetra-FeIII substituted sandwich-type unit [Fe4(H2O)10(B-β-SbW9O33)2]6− is built up of two trilacunary Keggin subunits [B-β-SbW9O33]9− sandwiching a rhomb-like {FeIII4} cluster, and then the disordered PrIII cations work as bridges that link adjacent sandwich-type units [Fe4(H2O)10(B-β-SbW9O33)2]6−, giving rise to the first 2-D extended sheet based on tungstoantimonate fragments and Fe–RE heterometallic cations. 2–5 are isomorphic and exhibit a discrete structure composed of a tetra-FeIII substituted sandwich-type unit [Fe4(H2O)10(B-β-SbW9O33)2]6− and two supporting [RE(H2O)8]3+ cations. The electrochemical and electrocatalytic properties of 1 and 2 have been investigated in detail in a 0.5 mol L−1 Na2SO4 + H2SO4 supporting electrolyte, and both 1 and 2 illustrate obvious electrocatalytic activity toward the reduction of NO2− and BrO3−.
Co-reporter:Hailou Li, Wen Yang, Yun Chai, Lijuan Chen, Junwei Zhao
Inorganic Chemistry Communications 2015 Volume 56() pp:35-40
Publication Date(Web):June 2015
DOI:10.1016/j.inoche.2015.03.012
•The Dawson-like polyoxometalate•The Dawson-like cerium(IV)-hybridizing selenotungstate•Dawson-like lanthanide-hybridizing selenotungstate•Electrochemical propertiesA novel cerium(IV)-hybridizing selenotungstate with Dawson-like structure Na13H7[Ce(SeW17O59)2]·31H2O (1) has been synthesized by reaction of Na2WO4·2H2O, Na2SeO3 and (NH4)2Ce(NO3)6 in the aqueous solution and characterized by elemental analysis, IR spectrum, UV spectrum, thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. To the best of our knowledge, 1 stands for 1:2-type Dawson-like selenotungstate constructed from two identical [SeW17O59]12 − moieties combined via one Ce4 + ion. The Ce4 + cation displays a distorted square prismatic geometry defined by eight oxygen atoms from two [SeW17O59]12 − moieties. In the [Ce(SeW17O59)2]20 − polyoxoanion, the {SeO3} trigonal pyramid encapsulated into the [SeW17O59]12 − fragment is situated on the side close to the Ce4 + ion. The TGA curve of 1 reveals two steps of weight loss between 25 °C and 700 °C. Furthermore, the electrochemical and the electrocatalytic properties of 1 have been measured by cyclic voltammetry (CV) in 0.5 M Na2SO4 + H2SO4 aqueous solution.A novel Dawson-like cerium(IV)-hybridizing selenotungstate Na13H7[Ce(SeW17O59)2]·31H2O (1) has been synthesized and characterized.
Co-reporter:Hailou Li, Bo Shao, Yanyan Li, Lijuan Chen, Junwei Zhao
Inorganic Chemistry Communications 2015 Volume 61() pp:68-72
Publication Date(Web):November 2015
DOI:10.1016/j.inoche.2015.08.023
•Organic–inorganic hybrid octamolybdates•Octamolybdate-based hybrids functionalized by 1,3-bis[tris(hydroxymethyl)methylamino]propane ligand•Electrocatalytic reduction of bromateTwo octamolybdate-based organic–inorganic hybrids functionalized by 1,3-bis[tris(hydroxymethyl)methylamino]propane (H6bthmap) Na2H4[γ-Mo8O26(H5bthmap)2]·2H2O (1) and [NH4]6{[Cu(H3bthmap)]2(β-Mo8O26)} (2) have been synthesized through the aqueous synthetic method and structurally characterized by elemental analyses, IR spectra, UV spectra, thermogravimetric (TG) analysis and single-crystal X-ray diffraction. X-ray crystallography reveals that 1 consists of a classic [γ-Mo8O26]4 − polyoxoanion decorated by two flexible [H5bthmap]− ligands through two O atoms from two [H5bthmap]− ligands and 2 contains a [β-Mo8O26]4 − polyoxoanion with bisupporting [Cu(H3bthmap)]− anions via two terminal O atoms from the [β-Mo8O26]4 − polyoxoanion. As far as we know, 1 and 2 represent the first octamolybdate-based hybrids with 1,3-bis[tris(hydroxymethyl)methylamino]propane ligands. The TG curves of 1 and 2 indicate two steps of weight loss and three steps of weight between 25 and 980 °C, respectively. Furthermore, the electrochemical and electrocatalytic properties of 1 and 2 have been investigated.Two octamolybdate-based hybrids functionalized by 1,3-bis[tris(hydroxymethyl)methylamino]propane (H6bthmap) Na2H4[γ-Mo8O26(H5bthmap)2]·2H2O and [NH4]6{[Cu(H3bthmap)]2(β-Mo8O26)} were synthesized and characterized.
Co-reporter:Jie Luo, Xing Ma, Lijuan Chen, Junwei Zhao
Inorganic Chemistry Communications 2015 Volume 54() pp:25-30
Publication Date(Web):April 2015
DOI:10.1016/j.inoche.2015.01.015
•Organic–inorganic hybrid silicotungstate•Organic–inorganic hybrid independent 1-D double-chain structure•Electrochemistry•MagnetismA novel organic–inorganic hybrid independent 1-D double-chain silicotungstate [Cu(biim)2][Cu(4,4′-bpy)(biim) (H2O)][α-SiW12O40]·3H2O (1, biim = 2,2′-biimidazole, 4,4′-bpy = 4,4′-dipyridine) has been successfully synthesized by reaction of Na10[A-α-SiW9O34]·18H2O, CuCl2·2H2O, EuCl3, biim and 4,4′-bpy under 160 °C hydrothermal environment and characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. The most remarkable structural feature of 1 is that two types of independent 1-D chains are paralleling and one is constructed from plenary Keggin [α-SiW12O40]4 − units and [Cu(biim)2]2 + linkers while the other is based on [Cu(biim)(H2O)]2 + cations and 4,4′-bpy connectors. The variable-temperature magnetic susceptibility of 1 shows the weak antiferromagnetic exchange interactions within CuII centers. Furthermore, the solid-state electrochemical properties of 1 have been also measured in 0.5 mol·L− 1 Na2SO4 + H2SO4 aqueous solution by entrapping it in a carbon paste electrode.An organic−inorganic hybrid independent 1-D double-chain Keggin-type silicotungstate with mixed ligands has been synthesized and characterized.
Co-reporter:Xiaoqiang Du, Jinli Zhao, Jiaqi Mi, Yong Ding, Panpan Zhou, Baochun Ma, Junwei Zhao, Jie Song
Nano Energy 2015 Volume 16() pp:247-255
Publication Date(Web):September 2015
DOI:10.1016/j.nanoen.2015.06.025
•Molecular semiconductor Na27[Fe11(H2O)14(OH)2(W3O10)2(α-SbW9O33)6] shows remarkable catalytic property for photocatalytic hydrogen evolution.•A H2 evolution rate of 820 μmol h−1 g−1 was achieved in the presence of catalyst without adding any photosensitizers and co-catalysts at neutral condition.•Six evidences proved that Fe11 is a true stable molecular catalyst during the photocatalytic hydrogen evolution.An unprecedented molecular polyanionic metal oxide cluster of eleven-FeIII substituted antimoniotungstate Na27[Fe11(H2O)14(OH)2(W3O10)2(α-SbW9O33)6]·103H2O(1) based on earth abundant elements has been successfully synthesized. A careful physical investigation of this molecule reveals that VB=−6.34 eV/CB=−4.39 eV, this unique physical properties ensures that 1 can be defined as a new type of nanoscale molecular semiconductor. This compound showed remarkable catalytic property for light driven H2 evolution activity. A H2 evolution rate of 820 μmol h−1 g−1 was achieved in the presence of 1 without adding any co-catalyst at neutral condition, which is a very high rate among all polyoxotungstate photocatalysts reported thus far. Six evidences proved that 1 is a true stable molecular catalyst during the photocatalytic hydrogen evolution.An unprecedented molecular polyanionic metal oxide cluster of eleven-FeIII substituted antimoniotungstate Na27[Fe11(H2O)14(OH)2(W3O10)2(α-SbW9O33)6]·103H2O showed remarkable catalytic property for light driven hydrogen evolution.
Co-reporter:Dr. Xin-Xiong Li;Dr. Wei-Hui Fang;Dr. Jun-Wei Zhao;Dr. Guo-Yu Yang
Chemistry - A European Journal 2015 Volume 21( Issue 6) pp:
Publication Date(Web):
DOI:10.1002/chem.201590021
Co-reporter:Jie Luo;Jian-Cai Liu;Bo Shao;Li-Juan Chen
Journal of Cluster Science 2015 Volume 26( Issue 6) pp:2005-2022
Publication Date(Web):2015 November
DOI:10.1007/s10876-015-0899-1
By introducing rigid aromatic N-ligands to the lacunary silicotungstate system under hydrothermal conditions, two new Keggin-type polyoxotungstate hybrids with copper–organic complexes [Cu(phen)(H2O)2]2[Cu(phen)2]2[α-SiW12O40]2·4H2O (1) and [Cu(4,4′-bpy)]3H[α-SiW12O40]·3 H2O (2) (phen = 1,10-phenanthroline, 4,4′-bpy = 4,4′-bipyridine) have been made and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The common architectural feature of 1 and 2 is that both comprise the plenary Keggin-type [α-SiW12O40]4− polyoxoanions modified by Cu–organic fragments containing various organic ligands. It should be pointed out that {[Cu(phen) (H2O)2][α-SiW12O40]}2+ and {[Cu(phen)2][α-SiW12O40]}2+ building units in 1 are alternately held together into an infinite 1-D chain fashion while the most striking characteristic of 2 is that two types of {–4,4′-bpy–Cu– 4,4′-bpy–Cu–}n 1-D polymeric chains are combined together by hexadentate [α-SiW12O40]4− polyoxoanions as the inorganic bridging ligands, giving birth to the aesthetic 3-D extended architecture. Moreover, electrochemical properties of 1 and 2 have been investigated.
Co-reporter:Dr. Xin-Xiong Li;Dr. Wei-Hui Fang;Dr. Jun-Wei Zhao;Dr. Guo-Yu Yang
Chemistry - A European Journal 2015 Volume 21( Issue 6) pp:2315-2318
Publication Date(Web):
DOI:10.1002/chem.201405290
Abstract
A novel 3-connected SrSi2-type 3D chiral framework constructed from hexa-NiII-cluster-substituted polyoxometalate (POM) units [Ni(enMe)2]3[WO4]3[Ni6(enMe)3(OH)3PW9O34]2⋅9H2O (1) (enMe=1,2-diaminopropane) has been made from a hydrothermal synthetic method. This POM represents the first 3D framework based on {Ni6PW9} units and {WO4} connectors.
Co-reporter:Yingjie Liu, Hailou Li, Jingli Zhang, Junwei Zhao, Lijuan Chen
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2015 Volume 134() pp:101-108
Publication Date(Web):5 January 2015
DOI:10.1016/j.saa.2014.06.076
•The mono-SmIII substituted phosphotungstate.•Organic–inorganic hybrid mono-lanthanide substituted polyoxometalates with amino acids.•IR spectra and UV spectra of 1:2-type [Sm(α-PW11O39)2]11− containing polyoxotungstates.•Solid-state photoluminescence of mono-SmIII substituted phosphotungstate.•Polyoxometalate-based ferroelectric material.An organic–inorganic hybrid mono-SmIII substituted phosphotungstate KNa3[HPro]7[Sm(α-PW11O39)2]·Pro·18H2O (1) (Pro = d-proline) has been synthesized in the conventional aqueous solution and structurally characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP-AES) analyses, IR spectra, UV spectra, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. The molecule of 1 consists of a classical 1:2-type [Sm(α-PW11O39)2]11− fragment and free d-proline components. It should be pointed out that the synergistic action between the in-situ formed chiral [Sm(α-PW11O39)2]11− fragment and chiral d-proline components results in the formation of the chiral 1. The luminescence emission of 1 reveals three characteristic bands that derive from the 4G5/2 → 6H5/2, 4G5/2 → 6H7/2 and 4G5/2 → 6H9/2 transitions of the SmIII cation as well as the synergistic contribution of the O → W transitions of [α-PW11O39]7− moieties and a π*–n or π*–π transitions of Pro. Its ferroelectric behavior has been measured.Graphical abstractAn organic–inorganic hybrid mono-SmIII substituted phosphotungstate with amino acids has been synthesized and IR, UV spectra, the photoluminescence spectra and ferroelectric behavior have been studied.
Co-reporter:Ling Huang ; Sa-Sa Wang ; Jun-Wei Zhao ; Lin Cheng ;Guo-Yu Yang
Journal of the American Chemical Society 2014 Volume 136(Issue 21) pp:7637-7642
Publication Date(Web):May 12, 2014
DOI:10.1021/ja413134w
Synergistic directing roles of six lacunary fragments resulted in an unprecedented Zr24-cluster substituted poly(polyoxotungstate) Na10K22[Zr24O22(OH)10(H2O)2(W2O10H)2(GeW9O34)4(GeW8O31)2]·85H2O (Na10K22·1·85H2O), which contains the largest [Zr24O22(OH)10(H2O)2] (Zr24) cluster in all the Zr-based poly(polyoxometalate)s to date. The most remarkable feature is that the centrosymmetric Zr24-cluster-based hexamer contains two symmetry-related [Zr12O11(OH)5(H2O)(W2O10H)(GeW9O34)2(GeW8O31)]16– trimers via six μ3-oxo bridges and was simultaneously trapped by three types of different segments of B-α-GeW9O34, B-α-GeW8O31, and W2O10. The other interesting characteristic is that there are two pairs of intriguing triangular atom alignments: one is composed of the Zr(2,4,6,8,11) and W21 atoms and the other contains the Ge(1–3), Zr(3,5,7,9,10,12) and W26 atoms, and the Zr5 atom is inside the triangle; a linking mode is unobserved. The oxygenation reactions of thioethers by H2O2 were evaluated when Na10K22·1·85H2O served as a catalyst. Results show that it is an effective catalyst for oxygenation of thioethers by H2O2. The unique redox property of oxygen-enriched polyoxotungstate fragments and Lewis acidity of the Zr cluster imbedded in Na10K22·1·85H2O provide a sufficient driving force for the catalytic conversion from thioethers to sulfoxides/sulfones.
Co-reporter:Jun-Wei Zhao, Jing-Li Zhang, Yan-Zhou Li, Jing Cao, and Li-Juan Chen
Crystal Growth & Design 2014 Volume 14(Issue 3) pp:1467-1475
Publication Date(Web):January 31, 2014
DOI:10.1021/cg500019g
Two unique organic–inorganic hybrid heteropolymolybdates with copper–aminoacid complexes [Cu(arg)2]2[(CuO6)Mo6O18(As3O3)2]·4 H2O (1) and [Cu(arg)2]3[TeMo6O24]·8H2O (2) (arg = l-arginine) have been prepared under the 110 °C hydrothermal environments and structurally characterized by elemental analyses, IR spectra, thermogravimetric (TG) analyses, and single-crystal X-ray diffraction. 1 stands for the first one-dimensional (1D) chain organic–inorganic hybrid arsenomolybdate constructed from lantern-shaped [(CuO6)Mo6O18(As3O3)2]4– units through dinuclear [Cu2(arg)4]4+ connectors, whereas 2 represents an unprecedented 1D chain organic–inorganic hybrid telluromolybdate built by Anderson-type [TeMo6O24]6– fragments via trinuclear [Cu3(arg)6]6+ bridges. Variable-temperature magnetic susceptibilities of 1 and 2 have been investigated and both illustrate the weak antiferromagnetic coupling within copper centers mediated by the carboxyl groups of arg ligands. Moreover, the solid-state electrochemical and electrocatalytic properties of 1 have been carried out in 1 mol L–1 H2SO4 aqueous solution by entrapping it in a carbon paste electrode. 1 displays apparent electrocatalytic activities toward the reduction of nitrite and bromate.
Co-reporter:Ying-Bing Lu, Fang-Mei Jian, Shuang Jin, Jun-Wei Zhao, Yong-Rong Xie, and Guo-Tian Luo
Crystal Growth & Design 2014 Volume 14(Issue 4) pp:1684-1694
Publication Date(Web):February 28, 2014
DOI:10.1021/cg401825f
Eight unprecedented Ln-NDC coordination polymers with BBI as templates {[HBBI][Ln(NDC)2(H2O)]·H2O [Ln = La (1), Pr (2)], [HBBI]2[Sm(NDC)2(H2O)]2·1/2H2O (3), and [HBBI][Ln(NDC)2(H2O)] [Ln = Eu (4), Gd (5), Tb (6), Dy (7), Er (8)] [Ln = lanthanide, H2NDC = 1,4-naphthalenedicarboxylic acid, BBI = bis(2,2′-biimidazole)]} have been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectra, and single-crystal X-ray diffraction. Complexes 1–8 crystallize in the monoclinic space group P21/c and display similar (8,8)-connected 3-D frameworks with different dinuclear Ln secondary building units due to the effect of Ln contraction and diverse coordination modes of NDC2– ligands. As the ionic radii of Ln ions decrease, the coordination numbers of Ln ions decrease from 10, to 9, to 8. The variable-temperature magnetic properties of 2–8 have been investigated. The strong fluorescent emissions of 4 demonstrate that ligand-to-EuIII energy transfer is efficient. In addition, thermogravimetric analyses and optical diffuse reflectance spectra of these compounds are also described.
Co-reporter:Junwei Zhao, Hailou Li, Yanzhou Li, Chunyang Li, Zhenling Wang, and Lijuan Chen
Crystal Growth & Design 2014 Volume 14(Issue 11) pp:5495-5505
Publication Date(Web):October 3, 2014
DOI:10.1021/cg500675g
Two types of unique oxalate-connective lanthanide-substituted isopolyoxotungstates, Na10[Ln2(C2O4)(H2O)4(OH)W4O16]2·30H2O (1) and K4Na16[Ln(C2O4)W5O18]4·60H2O (2) (Ln = EuIII, HoIII, ErIII, or TbIII), have been synthesized under conventional aqueous solution conditions and structurally characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, and thermogravimetric analyses. It should be pointed out that the utilization of different alkaline cations leads to the formation of two structural types. When only Na+ ions are present in the system, type 1 was obtained, while when Na+ and K+ ions are used, type 2 was found. Complex 1 is a double-oxalate-bridging di-Ln substituted Lindqvist dimer with a rectangle tetra-Ln cluster, whereas 2 is a single-oxalate-connective mono-LnIII Lindqvist tetramer with square tetra-Ln cluster. As far as we know, such di-Ln substituted Lindqvist fragment in 1 is observed for the first time. Moreover, 2 represents the first organic–inorganic hybrid square Ln-substituted isopolyoxotungstate. The solid-state luminescent properties of 1-Eu, 1-Tb, 2-Eu, and 2-Tb have been measured. 1-Eu and 2-Eu display intense, sharp, and narrow emission bands in the orange visible region that originate from the characteristic 5D0 → 7FJ transitions, and their fluorescence lifetimes are 1.18 and 1.20 ms, respectively. 1-Tb and 2-Tb exhibit green photoluminescence mainly derived from 5D4 → 7F5 transitions. The decay behavior of 1-Tb can be fitted to a biexponential function with lifetimes of τ1 = 0.43 ms and τ2 = 1.25 ms, whereas the decay behavior of 2-Tb can be fitted to single exponential function with the lifetime of 1.03 ms. Magnetic susceptibilities of 1 and 2 have been measured, and the decline of χMT upon cooling for 1 and 2 is mostly related to the progressive thermal depopulation of the excited state of Ln cations.
Co-reporter:Jun-Wei Zhao, Jing Cao, Yan-Zhou Li, Jing Zhang, and Li-Juan Chen
Crystal Growth & Design 2014 Volume 14(Issue 12) pp:6217-6229
Publication Date(Web):October 27, 2014
DOI:10.1021/cg5007988
By the routine aqueous solution method, a series of transition-metal–lanthanide heterometallic tungstoantimonates [Ln(H2O)8]2[Fe4(H2O)8(thr)2][B-β-SbW9O33]2·22H2O [Ln = PrIII (1), NdIII (2), SmIII (3), EuIII (4), GdIII (5), DyIII (6), LuIII (7), thr = threonine] were prepared and structurally characterized by multiple testing techniques. The common structural characteristic of 1–7 is that they are isomorphous and all consist of a [Fe4(H2O)8(thr)2(B-β-SbW9O33)2]6– subunit with two supporting [Ln(H2O)8]3+ cations on both sides. It should be pointed out that two thr ligands in the [Fe4(H2O)8(thr)2(B-β-SbW9O33)2]6– subunit substitute for two water ligands in the classical [Fe4(H2O)10(B-β-SbW9O33)2]6– polyoxoanion. As far as we know, 1–7 represents the first organic–inorganic tungstoantimonate hybrids consisting of transition metal and lanthanide cations and amino acid components. The fluorescence behavior of 4 has been measured and manifests the remarkable fluorescence feature resulting from the emission signature of EuIII cations. Furthermore, the solid-state electrochemistry and electrocatalytic performances of 1 have been measured in 0.5 mol L–1 Na2SO4+H2SO4 aqueous solution, and the results show that 1 illustrates comparatively apparent catalytic activities toward the BrO3– and H2O2 reduction. The magnetic properties of 3 and 6 have been studied.
Co-reporter:Yanzhou Li, Jie Luo, Lijuan Chen and Junwei Zhao
RSC Advances 2014 vol. 4(Issue 92) pp:50679-50692
Publication Date(Web):23 Sep 2014
DOI:10.1039/C4RA08045A
As an important ramification of polyoxometalates, germanotungstate (GT) chemistry has gradually developed as a new research focus and a challenging area, and has made great progress in the past decade due to a wide range of potential applications in various areas such as catalysis, magnetism, photochemistry and materials science. In this review, we mainly focus on three categories of metal-functionalized GTs: transition metal (TM)-substituted GTs (TMSGTs), rare earth (RE)-substituted GTs (RESGTs) and GT-based TM–RE heterometallic derivatives (GTTRHDs). We discuss their synthetic strategies, structural features and some properties involving magnetism, electrochemistry and catalysis. Finally, some perspectives on this field are also provided and some possible directions for future work are outlined.
Co-reporter:Rui-Qin Li, Yan-Ying Li, Bai-Feng Yang, Huan He, Jun-Wei Zhao, Guo-Yu Yang
Inorganic Chemistry Communications 2014 Volume 44() pp:191-194
Publication Date(Web):June 2014
DOI:10.1016/j.inoche.2014.03.033
•Sandwich-type germanotungstate.•2-D hexa-CuII substituted polyoxotungstate.•Hexa-CuII-containing polyoxotungstate with mixed amine ligand.•Germanotungstate with two kinds of hexa-CuII sandwiched units.A novel 2-D hexa-CuII substituted sandwich-type polyoxotungstate [Cu(H2O)4][Cu(dien)(H2O)2]2[Cu(dien)(H2O)]2[Cu6(en)2(H2O)2(B-α-HGeW9O34)2][Cu6(Hdien)2(H2O)2(B-α-HGeW9O34)2]·24 H2O (1, en = ethylenediamine, dien = diethylenetriamine) has been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. 1 represents the first 2-D inorganic–organic hybrid sandwich-type germanotungstate constructed by two kinds of hexa-CuII substituted sandwich-type POM hybrid units accompanying the mixed organoamine components in the structure. The TGA curve of 1 displays two continuous weight loss stages.A novel polyoxotungstate was made and characterized, in which two kinds of hexa-Cu sandwiched polyoxoanions, [Cu6(en)2(H2O)2(B-α-HGeW9O34)2] and [Cu6(Hdien)2(H2O)2(B-α-HGeW9O34)2], linked by [Cu(dien)(H2O)]2 + and [Cu(H2O)4]2 + complex bridges to form 2-D layer.
Co-reporter:Xuejun Liu, Hailou Li, Jie Luo, Xing Ma, Junwei Zhao
Synthetic Metals 2014 Volume 198() pp:267-273
Publication Date(Web):December 2014
DOI:10.1016/j.synthmet.2014.10.011
•3-D organic–inorganic hybrid polyoxovanadate framework.•Mixed-valent polyoxovanadate.•3-D transition-metal-complex bridging polyoxovanadate.Two 3-D organic–inorganic hybrid mixed-valent polyoxovanadates [Ni(en)2][VIV4VV2O14] (1) and [Cu(en)2][VIV2VV3O12.5] (2) (en = ethylenediamine) have been hydrothermally synthesized and characterized by elemental analyses, IR spectra, X-ray photoelectron spectroscopy (XPS) and single-crystal X-ray diffraction. The common feature of 1 and 2 is that both exhibit the 3-D organic–inorganic hybrid framework. It should be pointed out that the 3-D hybrid architecture of 1 is constructed from planar 2-D vanadium(IV/V)–oxygen layers through [Ni(en)2]2+ bridges, whereas the 3D hybrid framework of 2 is built by wavy 2-D vanadium(IV/V)–oxygen layers via [Cu(en)2]2+ connectors. The magnetic properties of 1 have been investigated and 1 behaves as the dominant antiferromagnetic interactions within VIV centers.Two 3-D organic–inorganic hybrid mixed-valent polyoxovanadates 1 and 2 have been prepared and characterized by elemental analyses, IR spectra, XPS, X-ray diffraction, and magnetic susceptibility.
Co-reporter:Qin Meng;Huan He;Bai-Feng Yang;Guo-Yu Yang
Journal of Cluster Science 2014 Volume 25( Issue 5) pp:1273-1282
Publication Date(Web):2014 September
DOI:10.1007/s10876-014-0705-5
An organic–inorganic hybrid polyoxovanadoborate K6(CH3NH3)4[V12B18O54(OH)6-(H2O)]·2en·12H2O (1, en = ethylenediamine) has been synthesized under hydrothermal conditions and characterized by IR spectroscopy, element analyses, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. Single-crystal structure analysis reveals that 1 consists of a cage-like polyoxovanadium borate [V12B18O54(OH)6(H2O)]10− cluster that is constructed from a puckered {B18O36(OH)6} ring sandwiched by two triangle {V6O18} units, in which a water molecule is confined in the middle of the cage-like cluster. Interestingly, 1 represents the rare example of extended 3-D framework constructed from [V12B18O54(OH)6-(H2O)]10− clusters through K+ cations.
Co-reporter:Bin Cai;Bai-Feng Yang;Huan He;Guo-Yu Yang
Journal of Cluster Science 2014 Volume 25( Issue 5) pp:1283-1293
Publication Date(Web):2014 September
DOI:10.1007/s10876-014-0706-4
Two novel hexa-nickel(II)-substituted Keggin-type {Ni6PW9}-based tungstophosphates [Ni6(μ3-Tris)(en)3(Pr)(damp)(H2O)2(B-α-PW9O34)]·10H2O (1) and [Ni6(μ3-Tris)(en)3(damp)2(H2O)2(B-α-PW9O34)]·7H2O (2) (en = ethylenediamine, Pr = CH3CH2COO−, damp = 2-aminoisobutyrate, Tris = pentaerythritol) were hydrothermally synthesized and characterized by IR spectra, elemental analyses, powder X-ray diffraction, thermogravimetric analyses, and single-crystal X-ray diffraction. Crystal data for 1: orthorhombic, Pca21, a = 21.6962(7) Å, b = 20.6398(5) Å, c = 14.7825(4) Å, β = 90º, V = 6619.7(3) Å3, Z = 4; for 2: orthorhombic, Pca21, a = 21.6978(9) Å, b = 20.6658(7) Å, c = 14.7767(4) Å, β = 90º, V = 6625.9(4) Å3, Z = 4. 1 consists of a {Ni6(μ3-Tris)(en)3(Pr)(damp)(H2O)2}9+ core and a [B-α-PW9O34]9− (PW9) unit and is covalently functionalized by one Pr and one damp, as well as en and Tris ligands. The structure of 2 is the same to 1 except that the Pr anion in 1 is substituted by the other damp ligand. Most interestingly, 1 contains four kinds of organic ligands, while 2 includes three kinds of organic ligands, which are first observed in polyoxometalate chemistry.
Co-reporter:Bin Cai;Bai-Feng Yang;Huan He;Guo-Yu Yang
Journal of Cluster Science 2014 Volume 25( Issue 4) pp:1047-1059
Publication Date(Web):2014 July
DOI:10.1007/s10876-014-0688-2
Hydrothermal reactions of trilacunary precursor A-α-AsW9O349− polyoxoanions and nickel ions in the presence of ethylenediamine (en = ethylenediamine) led to two new hexa-Ni-substituted Keggin-type tungstoarsenates [Ni6(μ3-OH)3(en)3(H2O)6(B-α-AsW9O34)]·6H2O (1) and [Ni6(μ3-OH)3(en)3(H2O)6(B-α-AsW9O34)]·10H2O (2), which have been characterized by elemental analyses, IR spectra, powder X-ray diffraction, thermogravimetric analyses and single-crystal X-ray diffraction. Crystal data for 1: hexagonal, R3c, a = b = 20.4379(5) Å, c = 21.5062(6) Å, β = 120º, V = 7779.8 (3) Å3 and Z = 6; for 2: momoclinic, P21/c, a = 13.4200(3) Å, b = 19.1428(5) Å, c = 22.8845(9) Å, β = 112.403(3)º, V = 5435.2(3) Å3 and Z = 4. Structural analyses reveal that the [Ni6(μ3-OH)3(B-α-AsW9O34)] clusters in 1 and 2 are covalently functionalized by neutral en ligands, in which two similar {Ni6(μ3-OH)3(en)3(H2O)6}9+ cores have been observed by our lab. Notably, 1 and 2 represent the highest number of substituted transition metal ions in all known lacunary Keggin-type polyoxotungstoarsenate monomers.
Co-reporter:Bin Cai;Bai-Feng Yang;Huan He;Guo-Yu Yang
Journal of Cluster Science 2014 Volume 25( Issue 4) pp:1069-1084
Publication Date(Web):2014 July
DOI:10.1007/s10876-014-0690-8
Four new hexa-nickel(II)-substituted Keggin-type tungstophosphates [Ni6(μ3-OH)3(oeen)3(H2O)3(B-α-PW9O34)]·6H2O (1, oeen = N-(2-hydroxyethyl)enediamine), [Ni6(μ3-OH)3(oeen)3(H2O)4(B-α-PW9O34)]2·13H2O (2), [Ni6(μ3-OH)3(oeen)2(tran)(H2O)3(B-α-PW9O34)]·3H2O (3, tran = 1,4,7-triazonane) and [Ni6(μ3-OH)3(oeen)2(tran)(H2O)2(B-α-PW9O34)]·6H2O (4) have hydrothermally made by controlling their reaction temperatures. 1–4 have been characterized by elemental analyses, IR spectra, powder X-ray diffraction, thermogravimetric analyses and single-crystal X-ray diffraction, respectively. Structural analyses reveal that they consist of {Ni6(μ3-OH)3(H2O)n}9+ cores and B-α-PW9O34 (PW9) units, and further are stabilized by organic neutral oeen/tran molecules. 1–3 are isolated clusters while 4 is the 1D chain structure. It should be noted that the tran molecules in 3 and 4 are derived from the oeen molecules in the starting materials.
Co-reporter:Yan-Ying Li;Bai-Feng Yang;Huan He
Journal of Cluster Science 2014 Volume 25( Issue 4) pp:949-957
Publication Date(Web):2014 July
DOI:10.1007/s10876-013-0675-z
Two Co4-substituted sandwich-type polyoxometalates (H2en)9[Co4(H2O)2(PW9O34)2]{[Co(H2O)4][Co4(H2O)2(PW9O34)2]}·18H2O (1) and (H2en)5[Co4(H2O)2(H3GeW9O34)2]{[Co(H2O)4]2[Co4(H2O)2(H2GeW9O34)2]}·16H2O (2) (en = ethylenediamine) have been hydrothermally synthesized and characterized by IR spectra, elemental analyses, thermogravimetric analyses, powder X-ray diffraction and single-crystal X-ray diffraction. Single-crystal structure analysis reveals that the molecules of 1 and 2 contain two Co4-substituted sandwich-type polyoxoanions. This type of a molecular unit containing double polyoxoanions is very rare. From the viewpoint of supramolecular chemistry, the sandwich-type polyoxoanions in 1 and 2 can be further extended to 3-D frameworks via extensive hydrogen-bonding interactions.
Co-reporter:Yan-Ying Li;Qi Wei;Bai-Feng Yang;Guo-Yu Yang
Journal of Cluster Science 2014 Volume 25( Issue 2) pp:549-557
Publication Date(Web):2014 March
DOI:10.1007/s10876-013-0638-4
A tetra-CoII substituted sandwich-type polyoxotungstate (H2TED)2Cs4[Co4(H2O)2(B-α-HPW9O34)2]·28H2O (TED = triethylenediamine) has been hydrothermally synthesized and characterized by IR spectrum, elemental analysis, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction, respectively. Single-crystal structure analysis reveals that the tetra-CoII substituted sandwich-type phosphotungstate units [Co4(H2O)2(B-α-PW9O34)2]10− are combined together by Cs+ cations giving rise to the 3D framework with the “sqc876” 3D net.
Co-reporter:Jie Luo, Hailou Li, Xinxin Chen, Jianru Ma, Lijuan Chen, Junwei Zhao
Inorganic Chemistry Communications 2014 50() pp: 19-23
Publication Date(Web):
DOI:10.1016/j.inoche.2014.10.003
Co-reporter:Dr. Xin-Xiong Li;Dr. Wei-Hui Fang;Dr. Jun-Wei Zhao;Dr. Guo-Yu Yang
Chemistry - A European Journal 2014 Volume 20( Issue 52) pp:17324-17332
Publication Date(Web):
DOI:10.1002/chem.201404384
Abstract
Three novel hexa-Ni-substituted Dawson phosphortungstates [Ni6(en)3(H2O)6(μ3-OH)3(H3P2W15O56)]⋅14 H2O (1), [Ni(enMe)2(H2O)][Ni6(enMe)3(μ3-OH)3(H2O)6(HP2W15O56)]⋅ 10 H2O (2), and [Ni(enMe)2]3[Ni(enMe)2(H2O)][Ni(enMe)(H2O)2][Ni6(enMe)3(μ3-OH)3(Ac)2(H2O)(P2W15O56)]2⋅6 H2O (3) (en=ethylenediamine, enMe=1, 2-diaminopropane, Ac=CH3COO−) have been made under hydrothermal conditions and were characterized by IR spectroscopy, elemental analysis, diffuse reflectance spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. The common structural features of compounds 1–3 contain the similar hexa-Ni-substituted Dawson polyoxometalate (POM) units that can be viewed as a [Ni6(μ3-OH)3]9+ cluster capping on a [P2W15O56]12− fragment. Compounds 1 and 2 are two isolated clusters, whereas compound 3 is the first 3D POM framework constructed from hexa-Ni-substituted Dawson POM units and Ni(enMe) complex bridges. The preparations of compounds 1–3 not only indicate that triangle coplanar Ni6 clusters are very stable fragments in both trivacant Keggin and trivacant Dawson POM systems, but also offer that the hydrothermal technique can act as an effective strategy for making novel Dawson-type high-nuclear transition-metal cluster substituted POMs by combination of lacunary Dawson precusors with transition-metal cations in the tunable role of organic ligands. In addition, magnetic measurements illustrate that there exist overall ferromagnetic interactions in compound 3.
Co-reporter:Dr. Xin-Xiong Li;Dr. Wei-Hui Fang;Dr. Jun-Wei Zhao;Dr. Guo-Yu Yang
Chemistry - A European Journal 2014 Volume 20( Issue 52) pp:
Publication Date(Web):
DOI:10.1002/chem.201485262
Co-reporter:Yan-Ying Li;Dr. Jun-Wei Zhao;Qi Wei;Bai-Feng Yang;Huan He; Guo-Yu Yang
Chemistry – An Asian Journal 2014 Volume 9( Issue 3) pp:858-867
Publication Date(Web):
DOI:10.1002/asia.201301305
Abstract
Two unique organic–inorganic hybrid polyoxometalates constructed from Preyssler-type [Na(H2O)P5W30O110]14− ({P5W30}) subunits and TM/Ln–carboxylate–Ln connectors (TM=transition metal, Ln=lanthanide), KNa7[{Sm6Mn(μ-H2O)2(OCH2COO)7(H2O)18}{Na(H2O)P5W30O110}]⋅22 H2O (1) and K4[{Sm4Cu2(gly)2(ox)(H2O)24}{NaP5W30O110}]Cl2⋅25 H2O (2; gly=glycine, ox=oxalate) have been hydrothermally synthesized and characterized by elemental analyses, IR spectra, UV/Vis-NIR spectra, thermogravimetric analyses, power X-ray diffraction, and single-crystal X-ray diffraction. Compound 1 displays one interesting 3D framework built by three types of subunits, {P5W30}, [Sm2Mn(μ-H2O)2(OCH2COO)2(H2O)5]4+, and [Sm4(OCH2COO)5 (H2O)13]2+, whereas 2 also manifests the other intriguing 3D architecture created by three types of subunits, {P5W30}, [SmCu(gly)(H2O)8]4+, and [Sm2(ox)(H2O)8]4+. To our knowledge, 1 and 2 are the first 3D frameworks that contain {P5W30} units and TM/Ln–carboxylate–Ln connectors. The fluorescent properties of 1 and 2 have been investigated.
Co-reporter:Hai-Yan Zhao, Jun-Wei Zhao, Bai-Feng Yang, Huan He, and Guo-Yu Yang
Crystal Growth & Design 2013 Volume 13(Issue 12) pp:5169-5174
Publication Date(Web):November 8, 2013
DOI:10.1021/cg4014575
The reaction of trivacant Keegin germanotungstate [A-α-GeW9O34]10– with Mn2+ and Ce4+ cations in the presence of oxalate ligand under hydrothermal conditions led to the isolation of a novel organic–inorganic hybrid 3d–4f heterometallic germanotungstate K4Na4[Ce2(ox)3(H2O)2]2{[Mn(H2O)3]2[Mn4(GeW9O34)2(H2O)2]·14H2O (1) (ox = oxalate), which has been characterized by elemental analysis, IR spectroscopy, thermogravimetric (TG) analysis, and single-crystal X-ray crystallography. Interestingly, each tetra-MnII-substituted sandwich-type unit acts as 14-dentate ligands to link eight Ce3+ centers and six Mn2+ centers further into a three-dimensional (3D) architecture. The 3D structure can be considered as two parts: one is the two-dimensional layer formed by sandwich-type [Mn4(H2O)2(GeW9O34)2]12– fragments and Mn2+ linkers; the other layer is constructed from Ce3+ cations and oxalate bridges, and the two layers are combined together alternately through W–O–Ce–O–W linkers, resulting in the 3D framework. Notably, 1 exhibits the first 3d–4f 3D organic–inorganic hybrid framework constructed by sandwich-type TM-substituted polyoxoanions and mixed 3d and 4f metal linkers in POM chemistry.
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:Yong-Chao Liu, Chun-Hua Fu, Shou-Tian Zheng, Jun-Wei Zhao and Guo-Yu Yang
Dalton Transactions 2013 vol. 42(Issue 48) pp:16676-16679
Publication Date(Web):08 Oct 2013
DOI:10.1039/C3DT51786A
Three novel polyoxometalates (POMs) containing [Ni6(μ3-OH)3]9− and [P2W15O56]12− units were first made, showing the first hexa-nuclearity transition-metal substituted POMs (TMSPs) based on monomeric lacunary Dawson fragments, which further indicates that the hydrothermal technique can offer an effective way for making new TMSPs through lacunary POM fragments incorporated with high-nuclear TM clusters.
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:Yuye Li, Shuanbao Tian, YanZhou Li, Junwei Zhao, Pengtao Ma, Lijuan Chen
Inorganica Chimica Acta 2013 Volume 405() pp:105-110
Publication Date(Web):24 August 2013
DOI:10.1016/j.ica.2013.05.027
•Organic–inorganic hybrid CuII–LnIII heterometallic polyoxometalates.•2D organic–inorganic hybrid phosphotungstates.•2D 5-conneted polyoxometalate-based CuII–LnIII heterometallic network.Reactions of the trivacant polyoxotungstate Na9[A-α-PW9O34]·7H2O with CuCl2·2H2O and LnCl3 (Ln = SmIII, ErIII) in the presence of 1,2-diaminopropane (dap) have led to two organic–inorganic hybrid Cu–Ln heterometallic polyoxotungstates [Cu(dap)2(H2O)][Cu(dap)2]4.5[Sm(α-PW11O39)2]·5H2O (1) and [Cu(dap)2(H2O)][Cu(dap)2]4.5[Er(α-PW11O39)2]·4H2O (2). 1 and 2 are isomorphic and display the 2D 5-connected sheet constructed from alternating bis(undecatungstophosphate)lanthanate [Ln(α-PW11O39)2]11− units and [Cu(dap)2]2+ connectors, in which the [Ln(α-PW11O39)2]11– subunits act as 5-connected nodes and adjacent 2D sheets show the –AAA– packing mode. Furthermore, their thermogravimetric analyses and magnetic susceptibilities have been investigated.Two 2D Cu–Ln heterometallic polyoxometalate aggregates 1 and 2 have been prepared and characterized by elemental analyses, IR spectra, X-ray diffraction, thermogravimetric analyses and magnetic susceptibility.
Co-reporter:Shuanbao Tian, Yanzhou Li, Junwei Zhao, Pengtao Ma, Lijuan Chen
Inorganic Chemistry Communications 2013 Volume 33() pp:99-104
Publication Date(Web):July 2013
DOI:10.1016/j.inoche.2013.04.004
•Organic–inorganic hybrid sandwich-type germanotungstate.•Germanotungstate with discrete polyoxoanions and 1-D chains.•Ferromagnetic tetra-FeIII sandwiched germanotungstate.A novel organic–inorganic hybrid sandwich-type germanotungstate [enH2]8[Fe4(en)(α-GeW9O34)2] [Fe4(en)2(α-GeW9O34)2]·en·14H2O has been synthesized by reaction of K8Na2[A-α-GeW9O34]·25 H2O, FeCl3, Ce(NH4)4(SO4)4·4H2O and en (en = ethylenediamine) under hydrothermal conditions and characterized by elemental analyses, IR spectrum, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS) and single-crystal X-ray diffraction. To our knowledge, 1 represents the first organic–inorganic hybrid sandwich-type germanotungstate with discrete [Fe4(en)2(α-GeW9O34)2]8 − polyoxoanions and 1-D [Fe4(en)(α-GeW9O34)2]n8n − polymeric chains in polyoxometalate chemistry. Thermogravimetric curve of 1 between 25 and 700 °C indicates two steps of weight loss. Variable-temperature magnetic susceptibilities of 1 exhibit the ferromagnetic interactions within the belt-like tetra-FeIII clusters mediated by the oxygen bridges.The first sandwich-type germanotungstate hybrid with discrete [Fe4(en)2(α-GeW9O34)2]8 − polyoxoanions and 1-D [Fe4(en)(α-GeW9O34)2]n8n − polymeric chains has been synthesized, which exhibits the ferromagnetic interactions within the belt-like tetra-FeIII clusters.
Co-reporter:J. W. Zhao;Y. Y. Li;Y. H. Wang;D. Y. Shi
Russian Journal of Coordination Chemistry 2013 Volume 39( Issue 7) pp:519-523
Publication Date(Web):2013 July
DOI:10.1134/S1070328413060122
A 2D Strandberg-type phosphomolybdate hybrid [Cu(En)(EnH)]2[P2Mo5O23] · 3H2O (I) (En = ethylenediamine) has been successfully synthesized under hydrothermal conditions and structurally characterized by elemental analyses, IR spectrum, UV spectrum and single-crystal X-ray diffraction. The molecular structural unit of I consists of one Strandberg-type [P2Mo5O23]6− subunit, two [Cu(En)(EnH)]3+ cations and three lattice water molecules. The most remarkable feature of I is that each molecular structural unit is connected with adjacent four same units by four [Cu(En)(EnH)]3+ bridges constructing the 2D organic-inorganic hybrid sheet structure with a 4-connected topology. As far as we know, such 2D hybrid sheet structure constructed from Strandberg-type phosphomolybdate units and copper-organic cation bridges is very rare.
Co-reporter:Jingli Zhang, Jie Li, Lijie Li, Haozhe Zhao, Pengtao Ma, Junwei Zhao, Lijuan Chen
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2013 Volume 114() pp:360-367
Publication Date(Web):October 2013
DOI:10.1016/j.saa.2013.05.054
•Copper–lanthanide heterometallic germanotungstate.•IR spectra of copper–lanthanide heterometallic germanotungstates.•Photoluminescence spectra of germanotungstates.•The electrocatalytic activity for nitrite reduction.Two organic–inorganic hybrid copper–lanthanide heterometallic germanotungstates KNa2H7[enH2]3[Cu(en)2(H2O)]2[Cu(en)2]2{Cu(en)2[Eu(α-GeW11O39)2]2}·13H2O (1) and Na2H4[Cu(en)2(H2O)]2[Cu(en)2]6[Cu(en)2]{Cu(en)2[La(α-GeW11O39)2]2}·12H2O (2) have been hydrothermally synthesized by reaction of K8Na2[A-α-GeW9O34]·25H2O with CuCl2·2H2O and EuCl3/LaCl3 in the presence of en (en = ethylenediamine) and structurally characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. 1 exhibits the 1D chain motif built by tetrameric {[Cu(en)2(H2O)]2[Cu(en)2]2{Cu(en)2[Eu(α-GeW11O39)2]2}}16− moieties through square antiprismatic K+ cations while 2 displays the 1D architecture made by tetrameric [[Cu(en)2]6[Cu(en)2]{Cu(en)2[La(α-GeW11O39)2]2}]10− units via octahedral [Cu(en)2]2+ cations. Furthermore, the solid-state electrochemical and electrocatalytic properties of 1 have been investigated and 1 indicates the good electrocatalytic activity for nitrite reduction. In addition, the photoluminescence property of 1 has been investigated.Two 1-D copper–lanthanide heterometallic germanotungstate hybrids have been synthesized and IR spectra, the photoluminescence spectra and the electrocatalytic activity for nitrite reduction of 1 have been studied.
Co-reporter:Junwei Zhao, Yamin Cheng, Sensen Shang, Fang Zhang, Li Chen, Lijuan Chen
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2013 Volume 116() pp:348-354
Publication Date(Web):December 2013
DOI:10.1016/j.saa.2013.07.079
•Copper–lanthanide heterometallic coordination polymers containing 2,2′-bipyridyl-5,5′-dicarboxylic acid.•IR spectra of copper–lanthanide heterometallic coordination polymers.•X-ray photoelectron spectroscopy of copper and lanthanide cations.•Solid-state photoluminescence of copper–lanthanide heterometallic coordination polymers.Three new two-dimensional CuI–LnIII heterometallic coordination polymers [LnIIICu2I(Hbpdc)4]·Cl·xH2O [LnIII = LaIII, x = 8 (1); LnIII = PrIII, x = 9 (2); LnIII = EuIII, x = 8 (3)] (H2bpdc = 2,2′-bipyridyl-5,5′-dicarboxylic acid) have been prepared under hydrothermal conditions and structurally characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP–AES) analyses, IR spectra, X-ray photoelectron spectroscopy (XPS) and single-crystal X-ray diffraction. X-ray diffraction indicates that the isomorphic 1–3 display the two-dimensional sheet structure constructed from [CuI(Hbpdc)2]– fragments through Ln3+ connectors. Moreover, the solid-state photoluminescence measurements of 3 indicate that the EuIII ions, Hbpdc– ligands and CuI cations make contributions to its luminescent properties simultaneously.Three two-dimensional CuI–LnIII heterometallic coordination polymers based on 2,2′-dipyridyl-5,5′-dicarboxylate ligands have been synthesized and IR spectra, XPS spectra and the photoluminescence spectra have been studied.
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, 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: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: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: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:Weijia Niu, Dongying Shi, Junwei Zhao, Xiaomeng Cai, Lijuan Chen
Inorganic Chemistry Communications 2012 Volume 17() pp:79-83
Publication Date(Web):March 2012
DOI:10.1016/j.inoche.2011.12.019
A novel organic–inorganic hybrid hexa-NiII sandwiched germanotungstate [enH2]2[Ni(en)2]2{[Ni6(en)2(H2O)2] [B-α-GeW9O34]2}·14H2O (1) has been hydrothermally synthesized and structurally characterized. 1 consists of a hexa-nickel sandwiched polyoxoanion {[Ni6(en)2(H2O)2][B-α-GeW9O34]2}8 −, two discrete [Ni(en)2]2 + cations, two free diprotonated [enH2]2 + cations and fourteen lattice water molecules. Notably, the sandwich-type polyoxoanion {[Ni6(en)2(H2O)2][B-α-GeW9O34]2}8 − is constructed from two trivacant [B-α-GeW9O34]10 − Keggin moieties in a staggered fashion linked via a belt hexa-nickel cluster [Ni6(en)2(H2O)2]12 +. To our knowledge, 1 represents the first hexa-NiII substituted sandwich-type germanotungstate. 1 shows the occurrence of ferromagnetic interactions within nickel centers. The photocatalytic property of 1 has been investigated.An organic–inorganic hybrid hexa-nickel sandwiched germanotungstate has been hydrothermally synthesized and structurally characterized. The magnetic and photocatalytic properties have been investigated.Highlights► Sandwich-type Keggin germanotungstate. ► The hexa-nickel substituted sandwich-type germanotungstate. ► The ferromagnetic interactions within nickel centers. ► The photocatalytic property of germanotungstate.
Co-reporter:Yuye Li, Chunli Leng, Junwei Zhao, Sudi Chen, Pengtao Ma, Lijuan Chen
Inorganic Chemistry Communications 2012 Volume 25() pp:35-38
Publication Date(Web):November 2012
DOI:10.1016/j.inoche.2012.08.005
An organic–inorganic hybrid paratungstate [enH2]2[Cu(en)2]3[H2W12O42]·6H2O (1) (en = ethylenediamine) has been hydrothermally synthesized by reaction of Na2WO4·2H2O with CuCl2·2H2O in the presence of en and structurally characterized by elemental analyses, IR spectroscopy, UV spectrum, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and X-ray single-crystal diffraction. It is worth pointing out that 1 exhibits the 6-connected 3-D framework with the long topological (O'Keeffe) vertex symbol 4·4·64·4·4·4·4·64·4·4·4·64·4·4·4 for the [Cu(en)2]3[H2W12O42]4 − node, which gives the short vertex (Schläfli) symbol of 41263. To the best of our knowledge, such 6-connected 3-D open-framework constructed from paratungstate clusters is for the first time observed in polyoxometalate chemistry.An organic–inorganic hybrid paratungstate [enH2]2[Cu(en)2]3[H2W12O42]·6H2O has been synthesized and displays the first six-connected 3-D architecture constructed from paratungstate-based polyoxometalate units and [Cu(en)2]2 + connectors.Highlights► The paratungstate-based polyoxometalate units ► The organic–inorganic hybrid paratungstate ► Six-connected 3-D framework constructed from paratungstate-based polyoxometalate units and [Cu(en)2]2 + connectors
Co-reporter:Jie Luo, Chunli Leng, Lijuan Chen, Jing Yuan, Huiying Li, Junwei Zhao
Synthetic Metals 2012 Volume 162(17–18) pp:1558-1565
Publication Date(Web):October 2012
DOI:10.1016/j.synthmet.2012.06.020
Three organic–inorganic hybrid monolacunary Keggin silicotungstate-based 3d–4f heterometallic derivatives NaH[Cu(dap)2(H2O)][Cu(dap)2]4.5[Ln(α-SiW11O39)2]·7H2O (Ln = SmIII for 1, DyIII for 2, GdIII for 3) have been prepared by the hydrothermal reaction of Na10[A-α-SiW9O34]·18H2O, CuCl2·2H2O, LnCl3 and dap (dap = 1,2-diaminopropane) and characterized by elemental analyses, IR spectra and X-ray single-crystal diffraction. 1–3 display the novel 3D CuII–LnIII heterometallic frameworks with the scarce 5-connected (46·64) topology and their common features are that they all consist of 1:2-type [Ln(α-SiW11O39)2]13− subunits and [Cu(dap)2]2+ connectors. To the best of our knowledge, 1–3 represent the rare 3D organic–inorganic hybrid Keggin silicotungstate-based 3d–4f heterometallic derivatives. In addition, the photoluminescence properties of 1 and 2 have been investigated and the magnetic susceptibilities of 1–3 have been measured.Graphical abstractThree organic–inorganic hybrid monolacunary Keggin silicotungstate 3d–4f heterometallic derivatives have been synthesized and characterized. The photoluminescence and magnetic properties have been investigated.Highlights► Organic–inorganic hybrid polyoxometalate-based 3d–4f heterometallic derivatives. ► 3D organic–inorganic hybrid 3d–4f heterometallic silicotungstates. ► The photoluminescence properties of the Sm and DyIII ions. ► The magnetism of Cu–Ln heterometallic silicotungstates.
Co-reporter:Yun Liu, Qiang Wang, Lijuan Chen, Haozhe Zhao, Junwei Zhao
Synthetic Metals 2012 Volume 162(17–18) pp:1648-1653
Publication Date(Web):October 2012
DOI:10.1016/j.synthmet.2012.07.009
A novel organic–inorganic hybrid 3D framework based on neodymium oxalate–selenites [Nd2(SeO3)2(C2O4) (H2O)2]·2H2O (1) has been successfully synthesized under hydrothermal conditions and further characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP-AES), X-ray powder diffraction (XRPD), IR spectrum, thermal analysis, and X-ray single-crystal diffraction. X-ray structural analysis reveals that 1 features a square ring composed of two {Nd2O4C2} subunits bridged by two {SeO3}2− anions via the corner-sharing mode. Interesting, the rhombic {Nd2O2} units interconnected with each other generating the 1D zigzag chain structure, whereas adjacent 1D chains are bridged by {SeO3}2− groups forming the 2D network architecture, which are further linked together through oxalate ligands leading to the 3D framework. The magnetic behavior of 1 is mainly due to the splitting of the 10-fold degenerate 4I9/2 ground state affected by the crystal field perturbation and the progressive depopulation of the higher energy state upon cooling.Graphical abstractA novel organic–inorganic hybrid based on neodymium oxalate–selenite [Nd2(SeO3)2(C2O4) (H2O)2]·2H2O (1) has been hydrothermally synthesized, which displays the 3-D porous framework constructed from {SeO3}2− groups and oxalate ligands.Highlights► The organic–inorganic hybrid 3D porous framework. ► Neodymium oxalate–selenites. ► Lanthanide(Ln)-containing selenites. ► The neodymium magnetism.
Co-reporter:Dongying Shi, Sensen Shang, Lijuan Chen, Xiaomeng Cai, Xiaoying Wang, Junwei Zhao
Synthetic Metals 2012 Volume 162(11–12) pp:1030-1036
Publication Date(Web):July 2012
DOI:10.1016/j.synthmet.2012.03.013
The hydrothermal reactions of Na8[A-α-HAsW9O34]·11H2O with CuCl2·2H2O, LnCl3 in the presence of ethylenediamine (en) lead to three novel 2D organic–inorganic hybrid CuII–LnIII heterometallic arsenotungstates Na3[Cu(en)2(H2O)][Cu(en)2]1.5[H3Ln(α-AsW11O39)2]·xH2O (Ln = DyIII, x = 5 (1); Ln = GdIII, x = 4 (2); Ln = LaIII, x = 5.5 (3)), which have been characterized by elemental analyses, IR spectra, optical diffuse reflectance spectra, thermogravimetric analyses and single-crystal X-ray diffraction. 1–3 are isomorphic and exhibit the unique 2D honeycomb (6,3)-network topology constructed from sandwich-type [H3Ln(α-AsW11O39)2]8− units through [Cu(en)2]2+ linkers. To the best of our knowledge, 1–3 represent rare 2D organic–inorganic hybrid CuII–LnIII heterometallic arsenotungstates. The photocatalytic measurements show that 1–3 can to some extent inhibit the photodegradation of rhodamine-B. Moreover, magnetic measurements demonstrate that there are the weak ferromagnetic behaviors in 1 and 2.Graphical abstractThree novel 2D organic–inorganic hybrid CuII–LnIII heterometallic arsenotungstates have been hydrothermally synthesized and structurally characterized. The photocatalytic, photoluminescence and magnetism preperties have been investigated.Highlights► CuII–LnIII heterometallic polyoxometalates. ► 2D organic–inorganic hybrid arsenotungstates. ► 2D (6,3)-network topology consisting of sandwich-type units. ► The photodegradation of rhodamine-B. ► The photoluminescence of the DyIII ion. ► Magnetism.
Co-reporter:X. R. Pei;Y. Y. Li;D. Y. Shi;J. Luo
Russian Journal of Coordination Chemistry 2012 Volume 38( Issue 2) pp:99-105
Publication Date(Web):2012 February
DOI:10.1134/S1070328412010083
A new 1D organic-inorganic hybrid monocopper substituted Dawson-type arsenotungstate (H2En)0.5[Cu(En)2]0.5{[Cu(En)2(H2O)]2[Cu(En)2](α1-As2W17CuO61)} · 8H2O (I) has been hydrothermally synthesized by the reaction of Na8[A-α-HAsW9O34] · 11H2O, CuCl2 · 2H2O, YCl3, with enthylenediamine (En) and characterized by elemental analyses, IR spectra, UV spectra, powder X-ray diffraction, thermogravimetric analysis, as well as single-crystal X-ray diffraction. Single-crystal structural analysis shows that I displays an interesting 1D chain constructed from [α1-As2W17CuO61]8− subunits by means of common oxygen atoms and [Cu(En)2]2+ bridges. It should be noted that the structural transformation of the trivacant Keggin polyoxoanion [A-α-AsW9O34]9− to the monovacant Dawson [α-As2W17O61]10− polyoxoanion was observed. The TG curve of I exhibits three stages of weight loss.
Co-reporter:Dongying Shi, Suzhi Li, Junwei Zhao, Weijia Niu, Sensen Shang, Yanzhou Li, Pengtao Ma, Lijuan Chen
Inorganic Chemistry Communications 2012 20() pp: 277-281
Publication Date(Web):
DOI:10.1016/j.inoche.2012.03.027
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: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: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: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: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: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:H. L. Cheng;D. Y. Shi;J. W. Zhao;Z. D. Geng
Russian Journal of Coordination Chemistry 2011 Volume 37( Issue 4) pp:
Publication Date(Web):2011 April
DOI:10.1134/S1070328411030031
A novel 3D 3d–4f heterometallic polymer Pr4(H2O)9Cu3.5Cl0.5(Bpdc)6.5(OH)2 · 5H2O (I) (H2Bpdc = 2,2′-bipyridyl-5,5′-dicarboxylic acid) has been hydrothermally synthesized by the reaction of CuCl2 · 2H2O, PrCl3, H2Bpdc, TAA (TAA = 1H-tetrazolyl-1-acetic acid) and glacial acetic acid and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Single-crystal structural analysis shows that I displays an interesting heterometallic 3D coordination framework constructed from 2D praseodymium-oxygen layers and [Cu(Bpdc)2]3− and [CuCl(Bpdc)]2− pillars. The photofluorescence properties of I have been investigated.
Co-reporter:Y. Liu;D. Y. Shi;J. W. Zhao;X. Y. Wang
Russian Journal of Coordination Chemistry 2011 Volume 37( Issue 9) pp:
Publication Date(Web):2011 September
DOI:10.1134/S1070328411080082
A novel 2D organic-inorganic hybrid 3d–4f polyoxometalate [Cu(Dap)2(H2O)][Cu(Dap)2]4.5[Gd(α-PW11O39)2] · 5H2O (I) (Dap = 1,2-diaminopropane) built by [Gd(α-PW11O39)2]11− units and [Cu(Dap)2]2+ bridges has been synthesized hydrothermally by the reaction of GdCl3, CuCl2 · 2H2O, Na9[A-α-PW9O34] · 7H2O, and Dap and characterized by elemental analysis, IR spectrum, UV spectrum, powder X-ray diffraction, and single-crystal X-ray diffraction. Single-crystal structural analysis shows that I displays an interesting 2D 3d–4f heterometallic sheet architecture with a 5-connected topology constructed from 1: 2-type [Gd(α-PW11O39)2]11− subunits and [Cu(Dap)2]2+ bridges. To the best of our knowledge, I represents a rare organic-inorganic hybrid 2D 3d–4f heterometallic monovacant Keggin phosphotungstate.
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: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: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:Jiancai Liu, Jie Luo, Qing Han, Jing Cao, Lijuan Chen, You Song and Junwei Zhao
Journal of Materials Chemistry A 2017 - vol. 5(Issue 8) pp:NaN2055-2055
Publication Date(Web):2017/01/19
DOI:10.1039/C6TC05479J
A neoteric 1-D sinusoidal tungstoantimonate (TA) Na2H4{[Mn(H2O)3]3[Mn(H2O)2]2[Mn(H2O)][Mn(C2O4)]3[B-α-SbW9O33]2}·31H2O (1) was synthesized from the reaction of Na9[B-α-SbW9O33]·19.5H2O with MnCl2·4H2O with the assistance of oxalic acid and structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, powder X-ray diffraction and thermal analyses. In 1, an unprecedented oxalate-bridging nona-MnII {[Mn(H2O)3]3[Mn(H2O)2]2[Mn(H2O)][Mn(C2O4)]3}12+ cluster is clamped by two trivacant Keggin [B-α-SbW9O33]9− fragments forming a unique nona-MnII-encapsulated sandwich-type species. In the sandwich belt, the internal hexa-MnII {[Mn(H2O)2]2[Mn(H2O)][Mn(C2O4)]3}6+ ring is alternately concatenated with three [Mn(H2O)3]2+ ions situated at three vertices of an equicrural triangle through oxalate linkers, completing an approximately coplanar nona-MnII core. More interestingly, adjacent nona-MnII-sandwiched TA units are interconnected by double MnII–C2O4 linkages, giving rise to the first inorganic–organic hybrid 1-D chain high-nuclear Mn-sandwiched TA. Furthermore, the zero-field-cooling/field-cooled magnetization and alternating current magnetic susceptibility measurements reveal the occurrence of long-range ferromagnetic ordering and spin-glass behavior in 1, which are further consolidated by the fitting of the Arrhenius law and the conventional critical scaling law of spin dynamics.
Co-reporter:Jun-Wei Zhao, Yan-Zhou Li, Li-Juan Chen and Guo-Yu Yang
Chemical Communications 2016 - vol. 52(Issue 24) pp:NaN4445-4445
Publication Date(Web):2016/02/05
DOI:10.1039/C5CC10447E
With the rapid development of science and technology and the trend of multidisciplinary pervasion, POM-based TM–RE heterometallic chemistry (POM = polyoxometalate, TM = transition-metal, RE = rare-earth) has become one of the most rapidly growing and challengeable areas of inorganic chemistry due to the impressive structural diversities, various chemical compositions and potential applications of these materials in magnetism, optics, electrochemistry, electrocatalysis and materials science. Over the past several years, continuous interest and persisting efforts have been dedicated to the preparation and exploration of POM-based TM–RE heterometallic derived materials (PTRHDMs), which have led to more than two hundred PTRHDMs. In this review, we summarize the structural types of reported PTRHDMs together with synthetic strategies, structural motifs and relevant functional applications. The exciting array of this emerging research theme presages continuous growth and great vitality. In the last section, some prospects of this branch are also presented and possible guidance for future work is outlined.
Co-reporter:Lijuan Chen, Fang Zhang, Xing Ma, Jie Luo and Junwei Zhao
Dalton Transactions 2015 - vol. 44(Issue 28) pp:NaN12612-12612
Publication Date(Web):2015/05/28
DOI:10.1039/C5DT00696A
Two classes of novel tetra-iron substituted sandwich-type arsenotungastates (ATs) with supporting lanthanide (Ln) pendants KNa2 [Ln(H2O)7][Fe4(H2O)10(B-β-AsW9O33)2]·21H2O [Ln = LaIII (1), PrIII (2), NdIII (3), SmIII (4)] and [Ln(H2O)8]2[Fe4(H2O)8(L-thr)2(B-β-AsW9O33)2]·20H2O [Ln = LaIII (5), PrIII (6), NdIII (7), SmIII (8), EuIII (9), GdIII (10), TbIII (11), DyIII (12), ErIII (13)] (L-thr = L-threonine) have been synthesized by the hydrothermal reaction of the [As2W19O67(H2O)]14− precursor with Fe3+ cations and Ln3+ cations in the presence of L-thr or L-leucine and L-alanine, and further characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. Structural analyses indicate that 1–4 display the inorganic 2-D sheet architecture constructed from tetra-iron sandwiched AT [Fe4(H2O)10(B-β-AsW9O33)2]6− fragments by bridging [Ln(H2O)7]3+ cations whereas the molecular structures of the isostructural 5–13 consist of an organic–inorganic hybrid tetra-iron substituted sandwich-type AT [Fe4(H2O)8(L-thr)2(B-β-AsW9O33)2]6− fragment and two pendant [Ln(H2O)8]3+ cations. As far as we know, 1–4 represent the rare inorganic 2-D extended ATs based on transition-metal substituted sandwich-type polyoxometalate units and Ln linkers and 5–13 are the first Fe–Ln heterometallic ATs with amino acid ligands. The solid state photoluminescence (PL) measurements of 9 and 11 have been performed at room temperature. The PL emission of 9 is mainly derived from the characteristic 5D0 → 7F2 (J = 4–0) transitions of the EuIII cations whereas the PL behavior of 11 stems from the common contribution of the 5D4 → 7FJ (J = 5–3) transitions of the TbIII ions and oxygen-to-metal (O → W) charge-transfer transitions of AT segments. The thermogravimetric (TG) analyses of 1–4 and 6–12 have been investigated.
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:Yong-Chao Liu, Chun-Hua Fu, Shou-Tian Zheng, Jun-Wei Zhao and Guo-Yu Yang
Dalton Transactions 2013 - vol. 42(Issue 48) pp:NaN16679-16679
Publication Date(Web):2013/10/08
DOI:10.1039/C3DT51786A
Three novel polyoxometalates (POMs) containing [Ni6(μ3-OH)3]9− and [P2W15O56]12− units were first made, showing the first hexa-nuclearity transition-metal substituted POMs (TMSPs) based on monomeric lacunary Dawson fragments, which further indicates that the hydrothermal technique can offer an effective way for making new TMSPs through lacunary POM fragments incorporated with high-nuclear TM clusters.
Co-reporter:Lei-Lei Li, Rui Pan, Jun-Wei Zhao, Bai-Feng Yang and Guo-Yu Yang
Dalton Transactions 2016 - vol. 45(Issue 30) pp:NaN11967-11967
Publication Date(Web):2016/05/25
DOI:10.1039/C6DT01629D
Six new lanthanide (Ln) germanate cluster organic frameworks (LnGeCOFs) derived from {Ln8Ge12} cage cluster units {[Nd(pza)2(H2O)] [Nd8Ge12(μ3-O)24E12(pza)(H2O)12]}·3H2O (1), {[Dy(CH3COO)(CO3)(H2O)]2[Dy8Ge12(μ3-O)24E12(H2O)12]}·11H2O (2), {[TbGeE(HO)2O(pza) (H2O)]2[Tb8Ge12(μ3-O)24E12(H2O)6]}·18H2O (3), {[DyGeE(HO)2O(C3H5NO2)(H2O)]2[Dy8Ge12(μ3-O)24E12(H2O)8]}·8H2O (4), {[Tb(pca)2 (H2O)]3[Tb8Ge12(μ3-O)24E12(H2O)4]}·(OH)3·10H2O (5) and {[Dy(pza)2(H2O)][Dy(pza)2(H2O)2][Dy(pza)3(H2O)][Dy8Ge12(μ3-O)24E12(pza)(HCOO) (H2O)6]}·5H2O (6) have been hydrothermally synthesized and structurally characterized. Increasing the amount of the second ligands can induce not only the assembly from 1 to 5, 6 based on Ln oxides as the starting sources, but also the assembly from 2 to 3, 4 based on Ln salts as the starting sources. The successful preparation of these LnGeCOFs suggests the importance of the second ligands in the structural construction of 1–6. To our knowledge, 1 is the first example that includes right- and left-handed helical chains among LnGeCOFs based on bis(carboxyethylgermanium)sesquioxide. 2, 4 and 6 are the first dysprosium incorporated organogermanates based on bis(carboxyethylgermanium)sesquioxide. 4 and 5 display very open framework structures with a solvent-accessible volume of 34.6% for 4 and 35.0% for 5. Moreover, the solid-state photoluminescence properties of 1, 3 and 5 have been investigated at room temperature and they exhibit the characteristic emission bands derived from Ln cations.
Co-reporter:Xing Ma, Hailou Li, Lijuan Chen and Junwei Zhao
Dalton Transactions 2016 - vol. 45(Issue 12) pp:NaN4960-4960
Publication Date(Web):2016/02/09
DOI:10.1039/C5DT05020K
Currently, transition-metal substituted polyoxotungstates (TMSPTs) have developed as a fast growing and challengeable subfamily of polyoxoxmetalates (POMs). Before 2005, the number of TM cores in TMSPTs was mostly lower than five. Since 2005, numerous inorganic or organic–inorganic TMSPTs with more than five TM cores (denoted as high-nuclear TMSPTs) have continuously been excavated and investigated. In this perspective, we endeavor to discuss the synthetic methodologies, structural diversities and relevant properties of the high-nuclear TMSPTs reported in the past decade. Future perspectives and opportunities on TMSPTs are included in the last section. This review is meant to provide fodder and guidance for further exploration and discovery of more high-nuclear TMSPTs with innovative architectures and remarkable functionality.
![Tungstate(3-),tetracosa-m-oxododecaoxo[m12-[phosphato(3-)-kO:kO:kO:kO':kO':kO':kO'':kO'':kO'':kO''':kO''':kO''']]dodeca-,hydrogen (1:3)](http://img.cochemist.com/ccimg/1400/1343-93-7.png)
![Tungstate(3-),tetracosa-m-oxododecaoxo[m12-[phosphato(3-)-kO:kO:kO:kO':kO':kO':kO'':kO'':kO'':kO''':kO''':kO''']]dodeca-,hydrogen (1:3)](http://img.cochemist.com/ccimg/1400/1343-93-7_b.png)
![Tungstate(6-),hexatriaconta-m-oxooctadecaoxobis[m9-[phosphato(3-)-kO:kO:kO:kO':kO':kO'':kO'':kO''':kO''']]octadeca-, hydrogen (1:6)](http://img.cochemist.com/ccimg/12500/12411-74-4.png)
![Tungstate(6-),hexatriaconta-m-oxooctadecaoxobis[m9-[phosphato(3-)-kO:kO:kO:kO':kO':kO'':kO'':kO''':kO''']]octadeca-, hydrogen (1:6)](http://img.cochemist.com/ccimg/12500/12411-74-4_b.png)
![Tungstate(10-), [m9-[orthosilicato(4-)-kO:kO:kO:kO':kO':kO'':kO'':kO''':kO''']]pentadeca-m-oxopentadecaoxonona-, sodium (1:10)](http://img.cochemist.com/ccimg/64700/64684-57-7.png)
![Tungstate(10-), [m9-[orthosilicato(4-)-kO:kO:kO:kO':kO':kO'':kO'':kO''':kO''']]pentadeca-m-oxopentadecaoxonona-, sodium (1:10)](http://img.cochemist.com/ccimg/64700/64684-57-7_b.png)
