Three polyoxovanadate-based metal-organic polyhedra (denoted as VMOP-1, -2, and -3), adopting isostructural discrete octahedral cage geometries, were successfully synthesized under solvothermal conditions. These structures are all built up from the same pentavanadate {V5O9Cl} cluster connected by linear bidentate ligands (H2L1 = H2BDC, H2L2 = H2BDC-NH2, H2L3 = H2BDC-Br), respectively.
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Henan Key Laboratory of Polyoxometalate Chemistry, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004, People's Republic of China.
The high-nuclearity polyoxovanadate-based carboxylate derivative KH[VV(OH)O(OOC(CH)COO)]·nHO (1) has been successfully synthesized by conventional aqueous methods and structurally characterized. The [VV(OH)O(OOC(CH)COO)] polyanion is built up from three cages: one {V(OH)O} cage and two identical [(VO)(OOC(CH)COO)] cages. Of the three cages, the {V(OH)O} is a purely inorganic polyoxovanadate cluster, whereas each of the [(VO)(OOC(CH)COO)] cages is a vanadium-based organic-inorganic hybrid cluster framed via four adipate ligands linking simultaneously to two triangular {V} units.
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Key Lab of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084, China. and State Key Laboratory of Natural and Biomimetic Drugs, Peking University, Beijing 100191, China.
A reaction strategy for the post-functionalization of hexavanadate derivatives is presented herein. In this study, five polyoxovanadate-based organic-inorganic hybrids TBA[VO{(OCH)CCOO(CH)CH}] (2), TBA[VO{(OCH)CCOO(CH)CH[double bond, length as m-dash]CH}] (3), TBA[VO{(OCH)CCOOCHCF}] (4), TBA[VO{(OCH)CCOO(CHCHO)CH}] (5), and TBA[VO{(OCH)CCOO(CH)OH}]·2CHCHOH (6) were successfully synthesized via esterification of carboxylic acid groups-containing TBA[VO{(OCH)CCOOH}] (1) with five alcohols possessing different functional groups. These hybrids were characterized by single crystal X-ray diffraction, IR, ESI-MS, H and C-NMR spectroscopies, and elemental analysis.
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Institute of Functional Material Chemistry, Key Lab of Polyoxometalate Science of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun, 130024, People's Republic of China.
Three polyoxovanadate-based metal-organic polyhedra (denoted as VMOP-1, -2, and -3), adopting isostructural discrete octahedral cage geometries, were successfully synthesized under solvothermal conditions. These structures are all built up from the same pentavanadate {V5O9Cl} cluster connected by linear bidentate ligands (H2L1 = H2BDC, H2L2 = H2BDC-NH2, H2L3 = H2BDC-Br), respectively.
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State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China.
Three unusual polyoxovanadate-based inorganic-organic hybrid complexes, [Zn(Im)(2)(DMF)(2)](2)[H(2)V(10)O(28)]·Im·DMF (1), [Zn(3)(Htrz)(6)(H(2)O)(6)][V(10)O(28)]·10H(2)O·Htrz (2) and {[Zn(3)(trz)(3)(H(2)O)(4)(DMF)](2)[V(10)O(28)]·4H(2)O}(n) (3) (Im = imidazole, Htrz = 1,2,4-triazole, DMF = N,N'-dimethylammonium) have been synthesized at room temperature via evaporative crystallization, and characterized by single-crystal X-ray diffraction. Complex 1 shows the structure of a discrete [V(10)O(28)](6-) cluster grafted by two [Zn(Im)(2)(DMF)(2)](2+) fragments through two bridged oxygen atoms, representing a rarely observed coordination mode. Complex 2 consists of a linear trinuclear Zn(II) unit bridging six Htrz ligands and a [V(10)O(28)](6-) cluster as the counter anion, where the extensive hydrogen-bonding interactions lead to {Zn(3)-V(10)}(SMF) and a special water layer involving (H(2)O)(36) rings, and consequently forms a unique 3D metal-organic-water supramolecular network.
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