一种新型钼钒酸盐的合成、结构和磁性表征

doi:10.3724/SP.J.1095.2014.30648

摘要/Abstract

摘要： 用水热方法合成了一个新型的钼钒多金属氧酸盐[PⅤMoⅥ7MoⅤVⅣ8O44][Ni(Phen)2OH]4·3H2O(1)，用元素分析、红外光谱和X射线单晶衍射等技术手段对化合物的晶体结构进行了表征。结果表明，该化合物属于三斜晶系，P-1空间群，a=1.51300(11) nm，b=1.74813(15) nm，c=2.58896(18) nm，α=72.842(4)°,β=89.240(5)°,γ=72.627(5)°，V=6.2233(8) nm3，Z=1，R1=0.0962,wR2=0.2572。化合物是高还原态的四帽α-Keggin结构钼钒多金属氧簇，通过簇阴离子4个钒帽上的端氧分别支撑4个镍过渡金属配合物，形成一个中性的多金属氧酸盐。多金属氧簇上的端氧与结晶水分子之间的强烈氢键使化合物形成了三维超分子结构。

关键词: 钼钒酸盐, 超分子, 水热合成, 磁性

Abstract: A new molybdenum-vanadium polyoxometalate [PⅤMoⅥ7MoⅤVⅣ8O44][Ni(Phen)2OH]4·3H2O(1) was prepared under hydrothermal conditions, and characterized by elemental analysis, IR and single crystal X-ray diffraction analysis. The title compound crystallized in a triclinic system, P-1 space group, a=1.51300(11) nm, b=1.74813(15) nm, c=2.58896(18) nm, α=72.842(4)°, β=89.240(5)°, γ=72.627(5)°, V=6.2233(8) nm3, Z=1, R1=0.0962, wR2=0.2572. Compound 1 is composed of a highly reduced tetra-capped pseudo-Keggin polyoxoanion supporting four transition metal complexes. There are many hydrogen bond among polyoxoanion and water molecules, which enable the formation of three dimensional supramolecular array.

Key words: molybvanudates, supramolecular, hydrothermal synthesis, magnetic properties

中图分类号:

O611.4

孙英华, 杨美玲, 郭庆芳, 陈迪, 姜晓宇. 一种新型钼钒酸盐的合成、结构和磁性表征[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30648.

SUN Yinghua1,2*, YANG Meiling1, GUO Qingfang3, CHEN Di1, JIANG Xiaoyu1. Synthesis, Structure Characterization and Magnetic Property of a New Molybdenum-vanadium Polyoxometalate[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30648.

参考文献

[1] Pope M T,Müller A. Polyoxometalate Chemistry:An Old Field with New Dimensioned in Several Disciplines[J]. Angew Chem Int Ed Eng,1991,30:34-48.

[2] Hagrman P J,Hagrman D,Zubieta J. Organic Inorganic Hybrid Materials:From “Simple” Coordination Polymers to Organodiamine-Templated Molybdenum Oxides[J]. Angew Chem Int Ed Engl,1999,38:2638-2684.

[3] Lei C,Mao J G,Sun Y Q,et al. A Novel Organic Inorganic Hybrid Based on an 8-Electron-ReducedKeggin Polymolybdate Capped by Tetrahedral, Trigonal Bipyramidal, and Octahedral Zinc:Synthesis and Crystal Structure of (CH3NH3)(H2bipy)[Zn4(bipy)3(H2O)2 MoⅤ8MoⅥ4O36(PO4)]·4H2O[J]. Inorg Chem,2004,43:1964-1968.

[4] Xu Y,Xu J Q,Zhang K L,et al. Keggin Unit Supported Transition Metal Complexes:Hydrothermal Synthesis and Characterization of [Ni(2,2′-bipy)3]1.5[PW12O40Ni(2,2′-bipy)2(H2O)]·0.5H2O and [Co(1,10′-phen)3]1.5[PMo12O40Co(1,10′-phen)2(H2O)]·0.5H2O[J]. Chem Commun,2000:153-154.

[5] Liu C M,Zhang D Q,Zhu D B,et al. Mixed Molybdenum-Vanadium Polyoxoanion-Bridged Trimetallic Nanocluster Complexes:Hydrothermal Syntheses and Crystal Structures of {MoⅥ6MoⅤ2VⅣ8O40(PO4)[Co(phen)2(H2O)]2}[Co2(phen)2(OH)2(H2O)4]1/2 and {MoⅥ5MoⅤ3VⅣ8O40(PO4)[Co(phen)(en)(H2O)]2}[Co (phen)3]·1.5H2O[J]. Cryst Grow Des,2003,3:363-368.

[6] Yuan M,Li Y,Wang E,Tian C,et al. Modified Polyoxometalates: Hydrothermal Syntheses and Crystal Structures of Three Novel Reduced and Capped Keggin Derivatives Decorated by Transition Metal Complexes[J]. Inorg Chem,2003,42:3670-3676.

[7] Luan G Y,Li Y G,Wang E B,et al. A New α-Keggin Type Polyoxometalate Coordinated to four Silver Complex Moieties:{PW9V3O40[Ag(2,2′-bipy)]2[Ag2(2,2′-bipy)3]2}[J]. Dalton Trans,2003:233-235.

[8] Lu Y K,Xu J N,Cui X B,et al. Modified Polyoxometalate:A Novel Bi-Antimony Capped, Highly Reduced α-Keggin Polyoxoanion[J]. Inorg Chem Commun,2010,13:46-49.

[9] Xiao L N,Qin Y J,Shi S Y,et al. Syntheses and Structural Characterization of Four New Organic-inorganic Hybrid Compounds Based on Bicapped Keggin Polyoxometalate {PMo12Sb2O40}[J]. Polyhedron,2012,38:113-120.

[10] Lu Y,Xu Y,Wang E B,et al. Novel Two-Dimensional Network Constructed from Polyoxomolybdate Chains Linked Through Copper-Organonitrogen Coordination Polymer Chains:Hydrothermal Synthesis and Structure of [H2bpy][Cu(4,4′-bpy)]2[HPCuMo11O39][J]. Cryst Grow Des,2005,1:257-260.

[11] LI Cuili,SUN Ping,LIU Shuxia. Synthesis and Crystal Structure of 1D Chain Like Compound[Cu(C10N2H8)2(H2O)]2{[Cu(C10N2H8)][Cr(OH)6Mo6O18]2}·10H2O[J]. J Northeast Normal Univ(Nat Sci Ed),2010,42(1):83-88（in Chinese）.

李翠莉，孙萍，刘术侠. 一维链状化合物[Cu(C10N2H8)2(H2O)]2{[Cu(C10N2H8)][Cr(OH)6Mo6O18]2}·10H2O的合成与晶体结构[J]. 东北师大学报(自然科学版)，2010,42(1):83-88.

[12] Brown I D,Altermatt D. Bond-valence Parameters Obtained from a Systematic Analysis of the Inorganic Crystal Structure Database[J]. Acta Crystallogr,Sect B：Struct Sci,1985,41:244-247.

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