Co-reporter:Yayu Dong, Zhimin Dong, Zhibin Zhang, Yunhai Liu, Weiwei Cheng, Hao Miao, Xingxiang He, and Yan Xu
ACS Applied Materials & Interfaces July 12, 2017 Volume 9(Issue 27) pp:22088-22088
Publication Date(Web):June 26, 2017
DOI:10.1021/acsami.7b07573
A POMs-based sorbent functionalized by phosphate groups: H33Na14MoV24MoVI2(PO4)11O73 has been successfully isolated under hydrothermal conditions. The cooperative assembly of the ring-shaped polyoxometalate structural building unit {P4Mo6} and MoO4 tetrahedra linkers gives rise to an unprecedented supersodalite cage containing approximately spherical cavities with a 8.76 Å diameter. As POMs-based inorganic material, compound 1 was first applied as sorbent to adsorb U(VI) from aqueous solution, exhibiting good stability, high efficiency, and selectivity. The maximum sorption capacity reaches 325.9 mg g–1, which may capture radionuclides through cooperative binding of the phosphate groups. The adsorbed U(VI) could be nearly drastically eluted when using 0.1 M Na2CO3 and the sorption capacity for U(VI) slightly decreased 10.16% through five successive sorption/desorption cycles. This work represents first application of POMs-based inorganic materials as sorbent to adsorb uranium from aqueous solution and provides a feasible approach for the entrapment and recovery of radionuclides.Keywords: adsorption; phosphate groups; POMs; super-sodalite cage; U(VI);
Co-reporter:Qingfang Lin;Xingxiang He;Weiwei Cheng;Yayu Dong
Crystal Growth & Design January 4, 2017 Volume 17(Issue 1) pp:347-354
Publication Date(Web):November 22, 2016
DOI:10.1021/acs.cgd.6b01576
A total of five three-dimensional Ln-Fe coordination polymers (CPs) [(CH3)2NH][(CH3)2NH2][Ln2Fe(SO4)4(L)]·3H2O (Ln = Eu, 1; Dy, 2; Gd, 3; Sm, 4; Er, 5; H2L = tartaric acid) have been successfully synthesized under solvothermal conditions and characterized by infrared spectroscopy, thermogravimetric analysis, elemental analyses, luminescence, and magnetic properties. Structural analysis indicates that the frameworks of 1–5 are constructed from novel [Ln8Fe4] rings. In the strcutures of 1–5, LnIII and FeIII ions interconnect through O donors of sulfate anions to generate a one-dimensional chain, and the adjacent chains are joined together by ligand [L]2– to form a two-dimensional zonary plane, which is further bridged by ligand [L]2– to give a new topology and named as “Xhd1”. Magnetic properties of 2 and 3 were investigated using variable temperature magnetic susceptibility, and weak ferromagnetic exchange between the FeIII and LnIII ions has been established for the Gd derivative. Meanwhile, we also studied luminescence spectra and luminescence lifetimes of 1 and 4 in the solid state at room temperature. The luminescence lifetime of 1 is 0.98 ms, which is significantly longer than the values in the reported Eu3+ coordination polymers.
Co-reporter:Mengjie Zhou, Dawei Yan, Yayu Dong, Xingxiang He, and Yan Xu
Inorganic Chemistry August 7, 2017 Volume 56(Issue 15) pp:9036-9036
Publication Date(Web):July 18, 2017
DOI:10.1021/acs.inorgchem.7b01057
A pair of novel chiral compounds based on homochiral 8-fold interpenetrated metal–organic frameworks (MOFs) and chiral polyoxometalates (POMs), formulated as d-[Cu(4,4′-bipy)1.5]4[Mo8O26] (d-1) and l-[Cu(4,4′-bipy)1.5]4[Mo8O26] (l-1) (4,4′-bipy = 4,4′-bipyridine), have been successfully synthesized and characterized by single crystal X-ray diffraction, infrared, thermogravimetric analysis, elemental analysis, and solid circular dichroism spectra. Structural analysis indicates that two compounds are enantiomers. The connection of copper cations and 4,4′-bipy ligands generates helical infinite chains, while adjacent chains are further linked by Cu–N bonds to form a three-dimensional interpenetrating framework with a (10,3)-a topology. Interestingly, the chiral [Mo8O26]4– polyanions are encapsulated in the chiral MOFs via sharing the oxygen atoms. Both d- and l-[Cu(4,4′-bipy)1.5]4[Mo8O26] crystallize in chiral space group C2221. Additionally, two compounds represent new examples of chiral self-assembly.
Co-reporter:Jie Shi;Yao Xiong;MengJie Zhou;Lu Chen
RSC Advances (2011-Present) 2017 vol. 7(Issue 87) pp:55427-55433
Publication Date(Web):2017/12/01
DOI:10.1039/C7RA12165B
Two Preyssler P5W30-based compounds: [Mn(H2O)2(DAPSC)]2{[Na3(H2O)2Mn0.5(H2O)4][Mn(H2O)(DAPSC)]2[H3P5W30O110]}·7.5H2O (1) and [Co(H2O)2(DAPSC)]{[Co(H2O)2(DAPSC)][Na1.5(H2O)2]}{[Na0.5(H2O)2Co0.5(H2O)4][Co(H2O)(DAPSC)]2[H4P5W30O110]}·6H2O (2) modified by Schiff base 2,6-diacetylpyridine bis(semicarbazone) (DAPSC) and transition metal (TM) ions have been successfully isolated and structurally characterized by IR spectroscopy, PXRD, and single-crystal XRD. Structural analysis reveals that compound 1 is composed of a {[Na3(H2O)2Mn0.5(H2O)4][Mn(H2O)(DAPSC)]2[H3P5W30O110]}4− architecture (Section A), two isolated [Mn(H2O)2(DAPSC)]2+ groups (Section B), and seven and a half lattice water molecules. Compounds 1–2 represent the first Preyssler-type compounds modified by Schiff base and TM ions. Additionally, the electrocatalytic and the third-order NLO properties have been investigated.
Co-reporter:Qingfang Lin;Jing Li;Yayu Dong;Guangpeng Zhou;You Song
Dalton Transactions 2017 vol. 46(Issue 30) pp:9745-9749
Publication Date(Web):2017/08/01
DOI:10.1039/C7DT01978E
Two lantern-shaped, high-nuclearity 3d–4f clusters {Ln52Ni52}(Ln = Gd and Dy) were synthesized by using iminodiacetic acid (H2IDA) and isonicotinic acid (HIN) as the co-ligand under solvothermal conditions. Magnetic studies show a large magnetocaloric effect (MCE) for the gadolinium analogue.
Co-reporter:Qingfang Lin;Yu Zhang;Weiwei Cheng;Ying Liu
Dalton Transactions 2017 vol. 46(Issue 3) pp:643-646
Publication Date(Web):2017/01/17
DOI:10.1039/C6DT04118C
Two novel core–shell Ni–Ln nanosized clusters, Na4(H3O)4[Nd38Ni42.5(IDA)42(OAc)4(CH3CH2OH)2(CO3)18(μ3-OH)62(μ3-O)6(H2O)12]Cl6·26H2O (1) and Na[Pr42Ni38(μ3-OH)71(μ3-O)4(IDA)38(NH2CH2COO)2(OAc)2(CH3CH2OH)2(CO3)16(H2O)6Cl7]Cl3·37H2O (2) (IDA = iminodiacetate), were successfully prepared using the Cl− anion and the flexible ligand iminodiacetic acid. Structural analysis indicates that the discrete dumbbell-shaped 3d–4f heterometallic cluster in 1 is constructed from two {Nd19Ni21} clusters connected by one {NiO6} unit, whereas the bowknot-shaped nanosized cluster is composed of two {Pr19Ni19} clusters ligated by two {Pr2} units and CO32− anions. The formation of both compounds indicates that Cl− ions play important roles and act not only as balance anions but also as template and bridging ligands. The magnetic properties of compounds 1 and 2 were investigated, and it was revealed that they display dominant antiferromagnetic exchange.
Co-reporter:Yayu Dong, Gonghao Hu, Hao Miao, Xingxiang He, Min Fang, and Yan Xu
Inorganic Chemistry 2016 Volume 55(Issue 22) pp:11621-11625
Publication Date(Web):November 10, 2016
DOI:10.1021/acs.inorgchem.6b02160
A novel high-nuclear nanosized cluster modified by conjugated organic ligands (pyridine and imidazole), [C5NH5]8[C3H5N2]2{[C5NH5]9[H31Mo12O24Co12(PO4)23(H2O)4]}·12H2O (1), has been successfully isolated under hydrothermal conditions and structurally characterized. Compound 1 consists of 12 CoII and 12 MoV ions linked by 23 {PO4} groups, exhibiting unprecedented nanosized ship-shaped clusters. The magnetic measurements reveal that compound 1 exhibits dominant antiferromagnetic interactions. Additionally, pyridine and imidazole ligands enhance the delocalized electron effects of clusters, and the third-order nonlinear-optical response of compound 1 is excellent.
Co-reporter:Xingxiang He, Ying Liu, Yun Lv, Yayu Dong, Gonghao Hu, Shuai Zhou, and Yan Xu
Inorganic Chemistry 2016 Volume 55(Issue 5) pp:2048-2054
Publication Date(Web):February 23, 2016
DOI:10.1021/acs.inorgchem.5b02372
A total of six three-dimensional chiral coordination compounds l- and d-[LnZn(IN)3(C2H4O2)]n (Ln = Eu, Sm, and Gd; HIN = isonicotinic acid) have been successfully synthesized under hydrothermal conditions without any chiral auxiliary and characterized by IR, TG, elemental analyses, and solid-state circular dichroism spectra. The structures of 1–6 were determined by single-crystal X-ray structural analysis, which shows that l-[LnZn(IN)3(C2H4O2)]n (Ln = Eu (1), Sm (2), and Gd (3)) crystallize in space group P6522 and are levogyrate. The chiral frameworks of l-[LnZn(IN)3(C2H4O2)]n are constructed from l-helical Ln-O-Zn cluster chains, while adjacent l-type helical −[Ln-O-Zn]n– chains are connected through IN– ligands. d-[LnZn(IN)3(C2H4O2)]n (Ln = Eu (4), Sm (5), and Gd (6)) crystallize in space group P6122, and their chiral frameworks consist of d-helical Ln-O-Zn cluster chains. The observed second-harmonic generation efficiencies of [EuZn(IN)3(C2H4O2)]n, [SmZn(IN)3(C2H4O2)]n, and [GdZn(IN)3(C2H4O2)]n are 0.4, 0.3, and 0.3 times that of urea, respectively. We also studied luminescence spectra and luminescence lifetimes of 1 and 2. The luminescence lifetimes of 1 and 2 are 1.18 ms, and 29.6 μs, respectively.
Co-reporter:Hao Miao, Yayu Dong, Ziwang Chen, Xingxiang He, Gonghao Hu and Yan Xu
Dalton Transactions 2016 vol. 45(Issue 32) pp:12717-12722
Publication Date(Web):14 Jul 2016
DOI:10.1039/C6DT02320G
Two new monosubstituted Keggin structural polyoxometalates [H5PMo11O39Zn(C5H5N)]·(C5H5N)5·H2O (1) and [H5PW11O39Co(C5H5N)]·(C5H5N)2·(C6H8N)2·1.5CH3OH (2) have been successfully synthesized under hydrothermal conditions. Structural analysis indicates that the polyoxoanion of compound 1 is a solvent molecule-bonded zinc-monosubstituted Keggin structural cluster, [PMo11O39Zn(C5H5N)]5−, while the polyoxoanion of compound 2 is a cobalt-monosubstituted phosphotungstate polyanion bonded with one pendant pyridine molecule. Both 1 and 2 show 3D supramolecular interpenetrating structures constructed of inorganic polyanion layers and organic layers. Very interestingly, compounds 1 and 2 exhibit excellent third-order NLO properties, and the TPA cross section σ of 1 and 2 is 2571.3 GM and 2876.3 GM, respectively.
Co-reporter:Gonghao Hu, Hao Miao, Hua Mei, Shuai Zhou and Yan Xu
Dalton Transactions 2016 vol. 45(Issue 19) pp:7947-7951
Publication Date(Web):15 Apr 2016
DOI:10.1039/C6DT00138F
The first polyoxometalates modified by a porphyrin-resembling planar Schiff base have been successfully designed and synthesized under hydrothermal conditions. The third-order NLO responses indicated that they are excellent third-order NLO materials. Their catalytic performances are also investigated.
Co-reporter:Zaizhao Zhang;Gonghao Hu
Chemical Research in Chinese Universities 2016 Volume 32( Issue 3) pp:329-333
Publication Date(Web):2016 June
DOI:10.1007/s40242-016-5429-7
A pure inorganic {P2Mo5O23}6– based cobalt complex [H8(H2O)16][Co(H2O)4(HP2Mo5O23)2] with a sandglass-like shape was synthesized and characterized by means of single-crystal X-ray diffraction, powder X-ray diffraction(PXRD), infrared spectroscopy(IR), thermogravimetry/differential scanning calorimetry(TG/DSC), ultraviolet- visible spectroscopy(UV-Vis) and cyclic voltammogram(CV). Single-crystal X-ray diffraction analysis reveals that the asymmetric unit of compound 1 consists of a half cobalt ion, one {P2Mo5O23}6– anion, two coordinated water molecules and eight lattice water molecules. It is especially intriguing to note that two {P2Mo5O23}6– clusters are symmetrical about the Co ion, like a sandglass. And a chair-like water cluster with an unprecedented centrosymmetric [H8(H2O)16]8+ can be observed in compound 1. Additionally, the electrochemical and catalytic properties of compound 1 were also investigated.
Co-reporter:Shuai Zhou, Hongxiang Wan, Gonghao Hu, Yu Zhang, Ying Liu, Hao Miao, Dunru Zhu and Yan Xu
Dalton Transactions 2015 vol. 44(Issue 18) pp:8605-8608
Publication Date(Web):25 Mar 2015
DOI:10.1039/C5DT01026H
A new vanadium sulfate, [H2N(CH3)2]19/3(en)[V5O5(μ3-O)4(SO4)4](SO4)2/3[HN(CH3)2]2/31, constructed from novel umbrella-like [VV(μ3-O)4VIV4O5(SO4)4(en)]5− anions was synthesized and structurally characterized using single-crystal X-ray analysis. The magnetic and optical studies of 1 indicate that the title compound exhibits significant ZFS (zero field splitting), interesting ferrimagnetic interactions and strong two photon absorption.
Co-reporter:Yayu Dong, Xiao Xu, Guangpeng Zhou, Hao Miao, GongHao Hu and Yan Xu
Dalton Transactions 2015 vol. 44(Issue 42) pp:18347-18353
Publication Date(Web):04 Sep 2015
DOI:10.1039/C5DT02710A
Three novel polyoxoanion-supported compounds modified by conjugated organic ligand tris(2-benzimidazylmethyl)amine (NTB) and nickel ions, [Ni(NTB)(H2O)]2(H2P2Mo5O23)·9.25H2O (1), [Ni(H2O)(NTB)]2(PMoVI11MoVO40)·4.5H2O (2) and [Ni(NTB)]2(Mo8O26)·9H2O (3), have been successfully synthesized under hydrothermal conditions at different pH values. The compounds 1–3 contain similar rigid concave surfaces composed of [Ni(NTB)]2+ cations, which connect with different clusters to form the first examples of metal-NTB-modified polyoxoanion-supported compounds. Transition metal-containing rigid concave surfaces successfully confine polyoxoanions in compounds 1–3. In the synthesis of the three compounds, the pH values play an important role in the formation of polyoxoanions and the stability of the compounds. Additionally, the third-order nonlinear optical properties (NLO) and electrochemical behaviors were also investigated.
Co-reporter:Hao Miao, Gonghao Hu, Jiuyu Guo, Hongxiang Wan, Hua Mei, Yu Zhang and Yan Xu
Dalton Transactions 2015 vol. 44(Issue 2) pp:694-700
Publication Date(Web):31 Oct 2014
DOI:10.1039/C4DT02993C
Two novel organic–inorganic hybrids, Na[PMoV8MoVI4O38(OH)2Zn4][pyim]2·1.5H2O [ε(pyim)2] (pyim = 2-(2-pyridyl)-imidazole) and [PMoV8MoVI4O37(OH)3Zn4]2[pyim]6·4H2O [ε2(pyim)6], based on ε-Zn Keggin units {ε-PMoV8MoVI4O40−x(OH)xZn4}, have been successfully synthesized under hydrothermal conditions by controlling the pH values. Structural analysis indicates that the framework of ε(pyim)2 is a 1D chain constructed by monomeric ε-Zn units modified by pyim ligands, while ε2(pyim)6 is an isolated structural compound with dimeric ε-Zn units modified by pyim ligands. This is the first isolated structure of the ε-Keggin POMs system. The luminescent and electrochemical properties of ε(pyim)2 and ε2(pyim)6 were investigated. ε2(pyim)6 also shows high catalytic activity for the esterification of phosphoric acid with equimolar lauryl alcohol to monoalkyl phosphate ester (MAP).
Co-reporter:Yu Zhang;Lian Huang;Hao Miao;Hong Xiang Wan;Hua Mei;Ying Liu; Yan Xu
Chemistry - A European Journal 2015 Volume 21( Issue 8) pp:3234-3241
Publication Date(Web):
DOI:10.1002/chem.201405178
Abstract
Two Ln26@CO3 (Ln=Dy and Tb) cluster-based lanthanide–transition-metal–organic frameworks (Ln MOFs) formulated as [Dy26Cu3(Nic)24(CH3COO)8(CO3)11(OH)26(H2O)14]Cl ⋅3 H2O (1; HNic=nicotinic acid) and [Tb26NaAg3(Nic)27(CH3COO)6(CO3)11(OH)26Cl(H2O)15]⋅7.5 H2O (2) have been successfully synthesized by hydrothermal methods and characterized by IR, thermogravimetric analysis (TGA), elemental analysis, and single X-ray diffraction. Compound 1 crystallizes in the monoclinic space group Cc with a=35.775(12) Å, b=33.346(11) Å, c=24.424(8) Å, β=93.993(5)°, V=29065(16) Å3, whereas 2 crystallizes in the triclinic space group P with a=20.4929(19) Å, b=24.671(2) Å, c=29.727(3) Å, α=81.9990(10)°, β=88.0830(10)°, γ=89.9940(10)°, V=14875(2) Å3. Structural analysis indicates the framework of 1 is a 3D perovskite-like structure constructed out of CO3@Dy26 building units and Cu+ centers by means of nicotinic acid ligand bridging. In 2, however, nanosized CO3@Tb26 units and [Ag3Cl]2+ centers are connected by Nic− bridges to give rise to a 2D structure. It is worth mentioning that this kind of 4d–4f cluster-based MOF is quite rare as most of the reported analogous compounds are 3d–4f ones. Additionally, the solid-state emission spectra of pure compound 2 at room temperature suggest an efficient energy transfer from the ligand Nic− to Tb3+ ions, which we called the “antenna effect”. Compound 2 shows a good two-photon absorption (TPA) with a TPA coefficient of 0.06947 cm GM−1 (1 GM=10−50 cm4 s photon−1), which indicates that compound 2 might be a good choice for third-order nonlinear optical materials.
Co-reporter:Yu Zhang;Lian Huang;Hao Miao;Hong Xiang Wan;Hua Mei;Ying Liu; Yan Xu
Chemistry - A European Journal 2015 Volume 21( Issue 8) pp:
Publication Date(Web):
DOI:10.1002/chem.201406071
Abstract
Invited for the cover of this issue is the group of Hua Mei and Yan Xu at Nanjing Tech University, China. The image depicts star-like {Tb26} clusters, which are simplified as blue balls, and Ag atoms, which are distributed in the MOF structure uniformly to give a lanthanide–MOF structure with good optical properties. Read the full text of the article at 10.1002/chem.201405178.
Co-reporter:Yu Zhang;Lian Huang;Hao Miao;Hong Xiang Wan;Hua Mei;Ying Liu; Yan Xu
Chemistry - A European Journal 2015 Volume 21( Issue 8) pp:
Publication Date(Web):
DOI:10.1002/chem.201590030
Co-reporter:Ying Liu;Yu Zhang;Gong Hao Hu;Shuai Zhou; Ruiqing Fan;Yulin Yang; Yan Xu
Chemistry - A European Journal 2015 Volume 21( Issue 29) pp:10391-10399
Publication Date(Web):
DOI:10.1002/chem.201501193
Abstract
Based on the isonicotinic acid (HIN=pyridine-4-carboxylic acid), seven lanthanide metal–organic frameworks (MOFs) with the formula [Ln(IN)2L] (Ln=Eu (1), Tb (2), Er (3), Dy (4), Ho (5), Gd (6), La (7), L=OCH2CH2OH) have been synthesized by mixing Ln2O3 with HIN under solvothermal conditions, and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, infrared spectroscopy, and fluorescence spectroscopy. Crystal structural analysis shows that compounds 1–6 are isostructural, crystallize in a chiral space group P212121, whereas compound 7 crystallizes in space group C2/c. Nevertheless, they all consist of new intertwined chains. Simultaneously, on the basis of the above-mentioned compounds, we have realized a rational design strategy to form the doped Ln MOFs [(EuxTb1−x)(IN)2L] (x=0.35 (8), x=0.19 (9), x=0.06 (10)) by utilizing TbIII as the second “rare-earth metal”. Interestingly, the photoluminescence of [(EuxTb1−x)(IN)2L] are not only adjustable by the ratios of Eu/Tb, but also temperature or excitation wavelength.
Co-reporter:Hao Miao, Hong-Xiang Wan, Ming Liu, Yu Zhang, Xiao Xu, Wei-Wei Ju, Dun-ru Zhu and Yan Xu
Journal of Materials Chemistry A 2014 vol. 2(Issue 32) pp:6554-6560
Publication Date(Web):18 Jun 2014
DOI:10.1039/C4TC00944D
Two high-nuclear wheel-shaped nanoscale clusters, [Co(H2O)6]{[C3H4N2]2[C5NH5]14[H15(Mo2O4)8Co16(PO4)14(HPO3)10(OH)3]}·5H2O (1) and [C3H5N2]4[C5NH5]2[Ni(H2O)6]{[C3H4N2]2[C5NH5]14[H18(Mo2O4)8Ni16(PO4)22(OH)6]}·11H2O (2), have been successfully synthesized employing the Py and Imi ligands as chemical modifiers. Both clusters take nanoscale wheel-like shapes, and the inorganic cores are wrapped up by the Py and Imi ligands acting as organic shells. In compounds 1 and 2, the polyoxoanion unit exhibits a new organic–inorganic hybrid polymolybdophosphate, representing the first two isolated POMs in the wheel-type {Mo/TM/P} materials, while Py and Imi ligands improve electric the delocalization effects of polyanions. It is worth noting that the molecular TPA cross section σ of compound 1 is 2.5 times that of compound 2, which demonstrates that the nonlinear optical property can also be improved by replacing part of the phosphate radicals with phosphite radicals through enhancing electron delocalization.
Co-reporter:Hao Miao, Xiao Xu, Wei-Wei Ju, Hong-Xiang Wan, Yu Zhang, Dun-Ru Zhu, and Yan Xu
Inorganic Chemistry 2014 Volume 53(Issue 6) pp:2757-2759
Publication Date(Web):February 24, 2014
DOI:10.1021/ic5000827
A dimeric Keggin polyoxometalate, [Cu(bpy)(μ2-OH)]4[(H2O)(bpy)2HPW11Cu2O39]2·2CH3CH2OH·10H2O (1), constructed from two dicopper(II)-substituted monovacant Keggin polyoxoanions bridged by a Cu4 cluster, has been hydrothermally synthesized. Magnetic analysis indicates predominantly an antiferromagnetic interaction between copper(II) centers. Compound 1 also shows very high catalytic activity for the esterification of phosphoric acid with equimolar lauryl alcohol to monoalkyl phosphate ester.
Co-reporter:Wei-Wei Ju, Hai-Tao Zhang, Xiao Xu, Yu Zhang, and Yan Xu
Inorganic Chemistry 2014 Volume 53(Issue 7) pp:3269-3271
Publication Date(Web):March 24, 2014
DOI:10.1021/ic500157x
Two enantiomerically pure polytungstates, Na2[(CH3)2NH2]3{Na⊂[CeIII(H2O)(CH3CH2OH)(l-tartH3)(H2Si2W19O66)]}·3.5H2O (l-1) and [(CH3)2NH2]7{Na⊂[CeIII(H2O)(CH3CH2OH)(d-tartH3)(Si2W19O66)]}·2.5H2O (d-1), were successfully synthesized. Structural analysis indicates that chiral tartrate ligands directly connect with novel lacunary [Si2W19O66]10– polytungstate units. Strong induced optical activity in the polyoxometalate (POM) units is manifested by circular dichroism spectroscopy. Z-scan analysis revealed that l-1 and d-1 are the first chiral POM-based complexes that exhibit two-photon absorption properties typical of the third-order nonlinear optical response.
Co-reporter:Hongxiang Wan, Congling Wang, Yu Zhang, Hao Miao, Shuai Zhou, and Yan Xu
Inorganic Chemistry 2014 Volume 53(Issue 19) pp:10498-10505
Publication Date(Web):September 19, 2014
DOI:10.1021/ic501573p
Four two-dimensional fully reduced polyoxovanadates, namely, [Cd(DAP)2]4[HVIII3VIV18P6O60(DAP)3(HOCH2CH2OH)]·10H2O (1), [Cd(DAP)2]4[HVIII3VIV18P6O60(DAP)3(CH3OH)]·11H2O (2), [Cd(DAP)2]4[HVIII3VIV18P6O60(DAP)3(CH3CH2OH)]·4H2O (3) and CoIII(DAP)3[CoII(DAP)2]3[VIII3VIV18P6O60(DAP)3(HOCH2CH2OH)]·14H2O (4) were synthesized by virtue of the reducing power of alkylamine in hydrothermal conditions. Single-crystal X-ray structural analysis, magnetic measurement, IR spectroscopy, elemental analysis, and thermogravimetric measurements were performed to analyze the structures and properties of these four compounds. Structural analysis indicates that the four compounds contain the same huge low-valent vanadium oxide anion cages [VIII3VIV18P6O60(DAP)3]9–, and the cages can catch different guest molecules. Four cages are linked by Co or Cd atoms to form a four-membered ring, while adjacent four-membered rings are connected to each other by sharing edges to make an inorganic–organic hybrid layer. The magnetic susceptibility measurements of four compounds indicate ferrimagnetic interactions between vanadium ions.
Co-reporter:Yu Zhang, Weiwei Ju, Xiao Xu, Yun Lv, Dunru Zhu and Yan Xu
CrystEngComm 2014 vol. 16(Issue 25) pp:5681-5688
Publication Date(Web):17 Apr 2014
DOI:10.1039/C4CE00513A
Two interesting mixed Eu3+/Y3+ lanthanide metal–organic frameworks, formulated as [EuY2(H2O)6(IN)3(ox)3]·H2O (1) and Eu3.5Y4.5(μ2-OH)8(IN)8(ox)4 (2) (HIN = isonicotinic acid; H2ox = oxalic acid), have been hydrothermally synthesized under the same initial reaction conditions except pH values. Such mixed Ln MOFs which contain two types of ligands are quite novel, and the pH value largely affects the topologies and Eu/Y ratios of the two compounds. Compound 1 exhibits a two-dimensional (2D) layered structure which is built up of [Ln2IN2]4+ units connected by oxalate ligands with a Eu/Y ratio of about 1:2, while in 2, the 2D Ln-ox metal–organic layers are connected by IN− ligands to give rise to a 3D framework with a Eu/Y ratio of about 1:1.3. Moreover, the photoluminescence properties of the two compounds indicate that fluorescence intensity of 1 is much greater than that of 2 due to the different levels of energy transfer and coordination environment.
Co-reporter:Hong-Xiang Wan, Wen-Tao Hou, Wei-Wei Ju, Yu Zhang, Hao Miao, You Song, Yan Xu
Inorganic Chemistry Communications 2014 Volume 45() pp:120-123
Publication Date(Web):July 2014
DOI:10.1016/j.inoche.2014.04.019
•Compound 1 is the first organic amine templated vanadyl pyrophosphate.•Compound 1 was synthesized at a relatively mild temperatures without any pyrophosphates.•There are two types of P-O-V helical chains in the structure of 1.•Magnetic susceptibility measurement of 1 indicates antiferromagnetic interactions between V4+ ions.The first organic amine templated vanadyl pyrophosphate, [H2N(CH3)2]2VO(P2O7) (1), has been synthesized at a relatively mild temperature (180 °C) under solvothermal conditions without any pyrophosphates. The structural analysis reveals that compound 1 is constructed by two types of helical chains and protonated dimethylamine cations. Two types of helical chains in 1 are connected through OVO linkages to make a double wave-like [VOP2O7]n chain. Magnetic susceptibility measurement of compound 1 indicates antiferromagnetic interactions between V4 + ions, while the observed SHG efficiency is 0.4 times of urea for 1.The compound, [H2N(CH3)2]2VO(P2O7) (1), has been synthesized at a relatively mild temperatures (180 °C) under solvothermal conditions without any pyrophosphates. The structural analysis reveals that two types of helical chains in 1 are connected through OVO linkages to make a double wave-like [VOP2O7]n chain. The observed SHG efficiency is 0.4 times of urea for 1.
Co-reporter:Yu Zhang;Lei Chen;Weiwei Ju
Chemical Research in Chinese Universities 2014 Volume 30( Issue 2) pp:194-199
Publication Date(Web):2014 April
DOI:10.1007/s40242-014-3368-8
Two new compounds, [ErAg(INA)2(C2O4)]·2H2O(1)(HINA=nicotinic acid) and [Tb0.8Y0.2Ag2(IN)4·(H2O)5]·NO3·2H2O(2)(HIN=isonicotinic acid), based on the {2} building units, have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, infrared spectroscopy, thermal analysis and powder X-ray diffraction(PXRD). Single-crystal X-ray diffraction data reveal that both compounds crystallized in the low-symmetry triclinic space group P\(\mathop {\rm{1}}\limits^{\rm{ - }} \). Compound 1 is a 3D heterometallic coordination framework based on {Er2} clusters, oxalate ligands and bridging [Ag(INA)] linkers, while compound 2 consists of 0D [Tb0.8·Y0.2Ag2(IN)4(H2O)5]2 subunits that give a 3D supramolecular structure through hydrogen bond interaction. The photoluminescent properties of both compounds(1 and 2) were studied.
Co-reporter:Gonghao Hu, Hao Miao, Hua Mei, Shuai Zhou and Yan Xu
Dalton Transactions 2016 - vol. 45(Issue 19) pp:NaN7951-7951
Publication Date(Web):2016/04/15
DOI:10.1039/C6DT00138F
The first polyoxometalates modified by a porphyrin-resembling planar Schiff base have been successfully designed and synthesized under hydrothermal conditions. The third-order NLO responses indicated that they are excellent third-order NLO materials. Their catalytic performances are also investigated.
Co-reporter:Hao Miao, Gonghao Hu, Jiuyu Guo, Hongxiang Wan, Hua Mei, Yu Zhang and Yan Xu
Dalton Transactions 2015 - vol. 44(Issue 2) pp:NaN700-700
Publication Date(Web):2014/10/31
DOI:10.1039/C4DT02993C
Two novel organic–inorganic hybrids, Na[PMoV8MoVI4O38(OH)2Zn4][pyim]2·1.5H2O [ε(pyim)2] (pyim = 2-(2-pyridyl)-imidazole) and [PMoV8MoVI4O37(OH)3Zn4]2[pyim]6·4H2O [ε2(pyim)6], based on ε-Zn Keggin units {ε-PMoV8MoVI4O40−x(OH)xZn4}, have been successfully synthesized under hydrothermal conditions by controlling the pH values. Structural analysis indicates that the framework of ε(pyim)2 is a 1D chain constructed by monomeric ε-Zn units modified by pyim ligands, while ε2(pyim)6 is an isolated structural compound with dimeric ε-Zn units modified by pyim ligands. This is the first isolated structure of the ε-Keggin POMs system. The luminescent and electrochemical properties of ε(pyim)2 and ε2(pyim)6 were investigated. ε2(pyim)6 also shows high catalytic activity for the esterification of phosphoric acid with equimolar lauryl alcohol to monoalkyl phosphate ester (MAP).
Co-reporter:Qingfang Lin, Jing Li, Yayu Dong, Guangpeng Zhou, You Song and Yan Xu
Dalton Transactions 2017 - vol. 46(Issue 30) pp:NaN9749-9749
Publication Date(Web):2017/06/27
DOI:10.1039/C7DT01978E
Two lantern-shaped, high-nuclearity 3d–4f clusters {Ln52Ni52}(Ln = Gd and Dy) were synthesized by using iminodiacetic acid (H2IDA) and isonicotinic acid (HIN) as the co-ligand under solvothermal conditions. Magnetic studies show a large magnetocaloric effect (MCE) for the gadolinium analogue.
Co-reporter:Hao Miao, Hong-Xiang Wan, Ming Liu, Yu Zhang, Xiao Xu, Wei-Wei Ju, Dun-ru Zhu and Yan Xu
Journal of Materials Chemistry A 2014 - vol. 2(Issue 32) pp:NaN6560-6560
Publication Date(Web):2014/06/18
DOI:10.1039/C4TC00944D
Two high-nuclear wheel-shaped nanoscale clusters, [Co(H2O)6]{[C3H4N2]2[C5NH5]14[H15(Mo2O4)8Co16(PO4)14(HPO3)10(OH)3]}·5H2O (1) and [C3H5N2]4[C5NH5]2[Ni(H2O)6]{[C3H4N2]2[C5NH5]14[H18(Mo2O4)8Ni16(PO4)22(OH)6]}·11H2O (2), have been successfully synthesized employing the Py and Imi ligands as chemical modifiers. Both clusters take nanoscale wheel-like shapes, and the inorganic cores are wrapped up by the Py and Imi ligands acting as organic shells. In compounds 1 and 2, the polyoxoanion unit exhibits a new organic–inorganic hybrid polymolybdophosphate, representing the first two isolated POMs in the wheel-type {Mo/TM/P} materials, while Py and Imi ligands improve electric the delocalization effects of polyanions. It is worth noting that the molecular TPA cross section σ of compound 1 is 2.5 times that of compound 2, which demonstrates that the nonlinear optical property can also be improved by replacing part of the phosphate radicals with phosphite radicals through enhancing electron delocalization.
Co-reporter:Yayu Dong, Xiao Xu, Guangpeng Zhou, Hao Miao, GongHao Hu and Yan Xu
Dalton Transactions 2015 - vol. 44(Issue 42) pp:NaN18353-18353
Publication Date(Web):2015/09/04
DOI:10.1039/C5DT02710A
Three novel polyoxoanion-supported compounds modified by conjugated organic ligand tris(2-benzimidazylmethyl)amine (NTB) and nickel ions, [Ni(NTB)(H2O)]2(H2P2Mo5O23)·9.25H2O (1), [Ni(H2O)(NTB)]2(PMoVI11MoVO40)·4.5H2O (2) and [Ni(NTB)]2(Mo8O26)·9H2O (3), have been successfully synthesized under hydrothermal conditions at different pH values. The compounds 1–3 contain similar rigid concave surfaces composed of [Ni(NTB)]2+ cations, which connect with different clusters to form the first examples of metal-NTB-modified polyoxoanion-supported compounds. Transition metal-containing rigid concave surfaces successfully confine polyoxoanions in compounds 1–3. In the synthesis of the three compounds, the pH values play an important role in the formation of polyoxoanions and the stability of the compounds. Additionally, the third-order nonlinear optical properties (NLO) and electrochemical behaviors were also investigated.
Co-reporter:Shuai Zhou, Hongxiang Wan, Gonghao Hu, Yu Zhang, Ying Liu, Hao Miao, Dunru Zhu and Yan Xu
Dalton Transactions 2015 - vol. 44(Issue 18) pp:NaN8608-8608
Publication Date(Web):2015/03/25
DOI:10.1039/C5DT01026H
A new vanadium sulfate, [H2N(CH3)2]19/3(en)[V5O5(μ3-O)4(SO4)4](SO4)2/3[HN(CH3)2]2/31, constructed from novel umbrella-like [VV(μ3-O)4VIV4O5(SO4)4(en)]5− anions was synthesized and structurally characterized using single-crystal X-ray analysis. The magnetic and optical studies of 1 indicate that the title compound exhibits significant ZFS (zero field splitting), interesting ferrimagnetic interactions and strong two photon absorption.
Co-reporter:Hao Miao, Yayu Dong, Ziwang Chen, Xingxiang He, Gonghao Hu and Yan Xu
Dalton Transactions 2016 - vol. 45(Issue 32) pp:NaN12722-12722
Publication Date(Web):2016/07/14
DOI:10.1039/C6DT02320G
Two new monosubstituted Keggin structural polyoxometalates [H5PMo11O39Zn(C5H5N)]·(C5H5N)5·H2O (1) and [H5PW11O39Co(C5H5N)]·(C5H5N)2·(C6H8N)2·1.5CH3OH (2) have been successfully synthesized under hydrothermal conditions. Structural analysis indicates that the polyoxoanion of compound 1 is a solvent molecule-bonded zinc-monosubstituted Keggin structural cluster, [PMo11O39Zn(C5H5N)]5−, while the polyoxoanion of compound 2 is a cobalt-monosubstituted phosphotungstate polyanion bonded with one pendant pyridine molecule. Both 1 and 2 show 3D supramolecular interpenetrating structures constructed of inorganic polyanion layers and organic layers. Very interestingly, compounds 1 and 2 exhibit excellent third-order NLO properties, and the TPA cross section σ of 1 and 2 is 2571.3 GM and 2876.3 GM, respectively.
Co-reporter:Qingfang Lin, Yu Zhang, Weiwei Cheng, Ying Liu and Yan Xu
Dalton Transactions 2017 - vol. 46(Issue 3) pp:NaN646-646
Publication Date(Web):2016/12/07
DOI:10.1039/C6DT04118C
Two novel core–shell Ni–Ln nanosized clusters, Na4(H3O)4[Nd38Ni42.5(IDA)42(OAc)4(CH3CH2OH)2(CO3)18(μ3-OH)62(μ3-O)6(H2O)12]Cl6·26H2O (1) and Na[Pr42Ni38(μ3-OH)71(μ3-O)4(IDA)38(NH2CH2COO)2(OAc)2(CH3CH2OH)2(CO3)16(H2O)6Cl7]Cl3·37H2O (2) (IDA = iminodiacetate), were successfully prepared using the Cl− anion and the flexible ligand iminodiacetic acid. Structural analysis indicates that the discrete dumbbell-shaped 3d–4f heterometallic cluster in 1 is constructed from two {Nd19Ni21} clusters connected by one {NiO6} unit, whereas the bowknot-shaped nanosized cluster is composed of two {Pr19Ni19} clusters ligated by two {Pr2} units and CO32− anions. The formation of both compounds indicates that Cl− ions play important roles and act not only as balance anions but also as template and bridging ligands. The magnetic properties of compounds 1 and 2 were investigated, and it was revealed that they display dominant antiferromagnetic exchange.
![[1,1'-Biphenyl]-4,4'-dicarboxylic acid, 3,3'-dihydroxy-](/data/chemimg/102600/861533-46-2.png)
![[1,1'-Biphenyl]-4,4'-dicarboxylic acid, 3,3'-dihydroxy-](/data/chemimg/102600/861533-46-2_b.png)
![5-(3,5-Dimethoxy-phenyl)-[1,3,4]thiadiazol-2-ylamine](http://img.cochemist.com/ccimg/383200/383130-39-0.png)
![5-(3,5-Dimethoxy-phenyl)-[1,3,4]thiadiazol-2-ylamine](http://img.cochemist.com/ccimg/383200/383130-39-0_b.png)
![Butanedioic acid, 2-[(1R)-1-phenylethyl]-3-(phenylmethyl)-, (2S,3S)-](http://img.cochemist.com/ccimg/337600/337518-33-9.png)
![Butanedioic acid, 2-[(1R)-1-phenylethyl]-3-(phenylmethyl)-, (2S,3S)-](http://img.cochemist.com/ccimg/337600/337518-33-9_b.png)
![5-(2,6-Difluoro-phenyl)-[1,3,4]thiadiazol-2-ylamine](http://img.cochemist.com/ccimg/300000/299933-69-0.png)
![5-(2,6-Difluoro-phenyl)-[1,3,4]thiadiazol-2-ylamine](http://img.cochemist.com/ccimg/300000/299933-69-0_b.png)
![Pyridine, 2,2'-[4-(4-chlorophenyl)-4H-1,2,4-triazole-3,5-diyl]bis-](http://img.cochemist.com/ccimg/204800/204759-27-3.png)
![Pyridine, 2,2'-[4-(4-chlorophenyl)-4H-1,2,4-triazole-3,5-diyl]bis-](http://img.cochemist.com/ccimg/204800/204759-27-3_b.png)
![3-?[[Bis(2-?pyridinylmethyl)?amino]?methyl]?-?2-?hydroxy-?5-?methylbenzaldehyde](/data/chemimg/192819-69-5.png)
![3-?[[Bis(2-?pyridinylmethyl)?amino]?methyl]?-?2-?hydroxy-?5-?methylbenzaldehyde](/data/chemimg/192819-69-5_b.png)
![Dibenzo[b,i][1,4,8,11]tetraazacyclotetradecine, 5,14-dihydro-6,15-dimethyl-8,17-diphenyl-](http://img.cochemist.com/ccimg/114000/113919-06-5.png)
![Dibenzo[b,i][1,4,8,11]tetraazacyclotetradecine, 5,14-dihydro-6,15-dimethyl-8,17-diphenyl-](http://img.cochemist.com/ccimg/114000/113919-06-5_b.png)
![Propanoic acid, 2-[4-[(6-chloro-2-quinoxalinyl)oxy]phenoxy]-, (2S)-](http://img.cochemist.com/ccimg/100800/100760-08-5.png)
![Propanoic acid, 2-[4-[(6-chloro-2-quinoxalinyl)oxy]phenoxy]-, (2S)-](http://img.cochemist.com/ccimg/100800/100760-08-5_b.png)
![Propanoic acid, 2-[4-[(6-chloro-2-quinoxalinyl)oxy]phenoxy]-, ethyl ester, (2S)-](http://img.cochemist.com/ccimg/100700/100646-52-4.png)
![Propanoic acid, 2-[4-[(6-chloro-2-quinoxalinyl)oxy]phenoxy]-, ethyl ester, (2S)-](http://img.cochemist.com/ccimg/100700/100646-52-4_b.png)
![1H-Benzimidazol-2-amine, N-[(2-chlorophenyl)methylene]-](http://img.cochemist.com/ccimg/76100/76061-11-5.png)
![1H-Benzimidazol-2-amine, N-[(2-chlorophenyl)methylene]-](http://img.cochemist.com/ccimg/76100/76061-11-5_b.png)
![[1,1'-BIPHENYL]-4,4'-DICARBOXYLIC ACID, 2,2'-DINITRO-, DIMETHYL ESTER](/data/chemimg/2294700/65235-35-0.png)
![[1,1'-BIPHENYL]-4,4'-DICARBOXYLIC ACID, 2,2'-DINITRO-, DIMETHYL ESTER](/data/chemimg/2294700/65235-35-0_b.png)
![1H-Benzimidazol-2-amine, N-[(4-methoxyphenyl)methylene]-](http://img.cochemist.com/ccimg/54200/54161-63-6.png)
![1H-Benzimidazol-2-amine, N-[(4-methoxyphenyl)methylene]-](http://img.cochemist.com/ccimg/54200/54161-63-6_b.png)
![[1,1'-Biphenyl]-4,4'-dicarboxylic acid, 2,2'-dinitro-](/data/chemimg/61700/41725-30-8.png)
![[1,1'-Biphenyl]-4,4'-dicarboxylic acid, 2,2'-dinitro-](/data/chemimg/61700/41725-30-8_b.png)
![Pyridine, 2,2'-[4-(4-methylphenyl)-4H-1,2,4-triazole-3,5-diyl]bis-](http://img.cochemist.com/ccimg/263600/263568-83-8.png)
![Pyridine, 2,2'-[4-(4-methylphenyl)-4H-1,2,4-triazole-3,5-diyl]bis-](http://img.cochemist.com/ccimg/263600/263568-83-8_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)
![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)
