Hydrothermal synthesis and characterization of (enH2)3.5[As8V14O42(PO4)]·2H2O

The compound (enH₂)_3.5[As₈V₁₄O₄₂(PO₄)]·2H₂O 1 (en=ethylenediamine) has been synthesized and characterized by means of elemental analysis, IR spectrum, ESR spectrum, XPS spectrum, TG analysis and single crystal X-ray diffraction analysis. The compound 1 crystallizes in monoclinic system, space group C2/c, β=105.59(3), Z=8 and R₁(wR₂)=0.0398(0.0885). The compound 1 is constructed from [As₈V₁₄O₄₂(PO₄)]⁷⁻ anions and H₂en cations linked through hydrogen bonds into a network. The [As₈V₁₄O₄₂(PO₄)]⁷⁻ cluster consists of 14 VO₅ square pyramids linked by 4 As₂O₅ handle-like units, and includes at its center an ordered PO₄³⁻ anion.     

Two unprecedented inorganic-organic boxlike and chainlike hybrids based on arsenic-vanadium clusters linked by nickel complexes

Two novel organic-inorganic hybrid arsenic-vanadates, [{Ni(en)₂}₄(4,4′-bipy)₄{Ni(H₂O)₂}]₂[As₈V₁₄O₄₂(NO₃)]₄·16H₂O 1 and [Ni(en)₂(H₂O)₂]₂[{Ni(en)₂(H₂O)}₂As₈V₁₄O₄₂(NO₃)][{Ni(en)₂}As₈V₁₄O₄₂(NO₃)]·6H₂O 2 are reported in this study. Crystal data for compound 1: Tetragonal, I4/m, a=27.507(4) Å, b=27.507(4) Å, c=22.101(4) Å; V=16722(5) Å³, Z=2, R(final)=0.0508. Crystal data for compound 2: Triclinic, P-1, a=11.530(2) Å, b=14.883(3) Å, c=21.330(4) Å, α=76.94(3)°, β=76.58(3)°, γ=69.54(3)°, V=3293.4(1) Å³, Z=1, R(final)=0.0559. The boxlike structure of compound 1 is designed from [{Ni(en)₂}₄(4,4′-bipy)₄{Ni(H₂O)₂}] sheets pillared by [α-As₈V₁₄O₄₂] clusters, which represents the first mixed-organic ligand-decorated tetrameric As-V-O cluster. Compound 2 is constructed from the rarely [β-As₈V₁₄O₄₂] clusters and Ni coordination complex fragments. The electrochemical property and magnetic property of compound 1 have been studied.     

Hydrothermal synthesis and structures of organic–inorganic hybrid solids based on arsenic-vanadate building blocks

Four novel organic–inorganic hybrid arsenic-vanadate complexes, [Cu(phen)][(As^VO₄)(V^V ₃O₇)(H₂O)] (1), [Cu(en)₂]₂[As₈V₁₄O₄₂(H₂O)]?·?2.5H₂O (2), [M(1,10-phen)₃]₂[As₈V₁₄O₄₂(H₂O)_0.5]?·?0.5H₂O (M?=?Mn, 3, Cd, 4) (1,10-phen?=?1,10-phenanthroline) have been hydrothermally synthesized for the first time and characterized by elemental analyses, XPS spectra, EPR spectra, IR spectra, TG analyses and single crystal X-ray diffraction. The structure of compound 1 consists of arsenic vanadate ribbons coordinated by the [Cu(phen)]²⁺ complex, while compounds 2 to 4 possess a spherical [As₈ ^IIIV₁₄ ^IVO₄₂]^4? cage with H₂O molecules encapsulated. The unexpected preparation 1 and the synthesis of compounds 2 to 4 on the basis of same polyoxoanion structures show that the pH value of the reaction plays a crucial role in controlling the basic architectures.     

无机-有机多金属砷钒氧簇合物的合成及研究进展

多金属砷钒氧簇合物由于具有结构多样性、优良的物理特性以及广泛的应用前景而引起人们的关注。该类簇合物的合成战略是将有机配体和过渡金属配合物连接到砷钒氧骨架上以获得各种新奇结构。按此策略人们合成出一系列新奇的无机有机砷钒氧簇合物。本文综述了多金属砷钒氧簇合物的合成方法、结构性质等方面的研究进展,并对其今后研究前景进行了展望。