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功能化金属氧化物簇：一系列新型的、用有机配体修饰的完全还原的杂多氧钒阳离子簇的合成、表征、晶体结构及磁性——[MVIV6O6[(OCH2CH2)2N(CH2CH2OH)]6]X（M = Li，X = Cl·LiCl；M = Na，X = Cl·H2O；M = Mg，X = 2Br·H2O；M = Mn、Fe，X = 2Cl；M = Co、Ni，X = 2Cl·H2O）

Functionalized metal oxide clusters: synthesis, characterization, crystal structures, and magnetic properties of a novel series of fully reduced heteropolyoxovanadium cationic clusters decorated with organic ligands--[MVIV6O6[(OCH2CH2)2N(CH2CH2OH)]6]X (M = Li, X = Cl x LiCl; M = Na, X = Cl x H2O; M = Mg, X = 2Br x H2O; M = Mn, Fe, X = 2Cl; M = Co, Ni, X = 2Cl x H2O).

作者信息

Khan M Ishaque, Tabussum Saadia, Doedens Robert J, Golub Vladimir O, O'Connor Charles J

机构信息

Department of Biological, Chemical and Physical Sciences, Illinois Institute of Technology, Chicago, Illinois 60616, USA.

出版信息

Inorg Chem. 2004 Sep 20;43(19):5850-9. doi: 10.1021/ic049417m.

DOI:10.1021/ic049417m

PMID:15360233

Abstract

A novel series of fully reduced heteropolyoxovanadium(IV) compounds, [MVIV6O6[(OCH2CH2)2N(CH2CH2OH)]6]X (1, M = Li, X = Cl x LiCl; 2, M = Na, X = Cl x H2O; 3, M = Mg, X = 2Br x H2O; 4, M = Mn, X = 2Cl; 5, M = Fe, X = 2Cl; 6, M = Co, X = 2Cl x H2O; 7, M = Ni, X = 2Cl x H2O), have been synthesized and characterized by FT-IR and UV-vis spectroscopies, thermogravimetric analysis, elemental analysis, manganometric titration, temperature-dependent magnetic susceptibility measurements, bond valence sum calculations, X-ray powder diffraction, and single-crystal X-ray diffraction analyses. The structures of the crystals are comprised of discrete units of fully reduced cluster cations, [MVIV6O6[(OCH2CH2)2N(CH2CH2OH)]6]n+, counterions (chloride or bromide), and water of crystallization (in the case of 2, 3, 6, 7). In each case the cluster ion is composed of a fully reduced cyclic [MV6N6O18] (M = Li, Na, Mg, Mn, Fe, Co, Ni) framework decorated with six triethanolamine ligands. Two arms of each triethanolamine ligand are coordinated to the metallacycle, and the third arm projects outward from the hexagonal ring. The [MV6N6O18] core adopts the Anderson-type structure. The cyclic core is comprised of a ring of six edge-sharing [VO5N] octahedra linked to a central [MO6] unit. The hexametalate ring contains six d1 ions [VIV] and shows remarkable flexibility to encapsulate a variety of metal centers Mn+ (Mn+ = Li+, Na+, Mg2+, Mn2+, Fe2+, Co2+, Ni2+) with different (dn) spins. The compounds show good thermal stability and exhibit interesting magnetic properties that make these magnetic clusters promising building blocks for constructing supramolecular structures and extended structure magnetic solids. Crystal data for 1; C36H78Cl2N6Li2O24V6, trigonal space group R, a = 13.7185(3) angstroms, c = 24.8899(8) angstroms, Z = 3. Crystal data for 2: C36H80ClN6NaO25V6, triclinic space group P, a = 11.1817(5) angstroms, b = 12.1612(5) angstroms, c = 21.5979(10) angstroms, alpha = 75.8210(10), beta = 78.8270(10), gamma = 71.1400(10), Z = 2. Crystal data for 4: C36H78Cl2N6MnO24V6, monoclinic, space group P2(1), a =11.2208(5) angstroms, b = 21.5041(9) angstroms, c = 11.8126(5), beta = 111.2680, Z= 2. Crystal data for 5: C36H78Cl2N6FeO24V6, monoclinic, space group P2(1), a = 11.3057(7) angstroms, b = 21.4372(13) angstroms, c = 11.8167(7) angstroms, beta = 111.4170, Z = 2.

摘要

合成了一系列新型的全还原杂多氧钒（IV）化合物，[MVIV6O6[(OCH2CH2)2N(CH2CH2OH)]6]X（1，M = Li，X = Cl·LiCl；2，M = Na，X = Cl·H2O；3，M = Mg，X = 2Br·H2O；4，M = Mn，X = 2Cl；5，M = Fe，X = 2Cl；6，M = Co，X = 2Cl·H2O；7，M = Ni，X = 2Cl·H2O），并通过傅里叶变换红外光谱（FT-IR）、紫外可见光谱、热重分析、元素分析、锰量滴定、变温磁化率测量、键价和计算、X射线粉末衍射和单晶X射线衍射分析对其进行了表征。晶体结构由全还原簇阳离子[MVIV6O6[(OCH2CH2)2N(CH2CH2OH)]6]n+的离散单元、抗衡离子（氯离子或溴离子）和结晶水（对于2、3、6、7而言）组成。在每种情况下，簇离子由一个全还原的环状[MV6N6O18]（M = Li、Na、Mg、Mn、Fe、Co、Ni）骨架组成，该骨架装饰有六个三乙醇胺配体。每个三乙醇胺配体的两条臂与金属环配位，第三条臂从六边形环向外伸出。[MV6N6O18]核采用安德森型结构。环状核由六个边共享的[VO5N]八面体环与一个中心[MO6]单元相连组成。六金属酸盐环包含六个d1离子[VIV]，并且对封装具有不同（dn）自旋的各种金属中心Mn+（Mn+ = Li+、Na+、Mg2+、Mn2+、Fe2+、Co2+、Ni2+）表现出显著的灵活性。这些化合物表现出良好的热稳定性，并展现出有趣磁性，这使得这些磁性簇成为构建超分子结构和扩展结构磁性固体的有前途的构建单元。1的晶体数据：C36H78Cl2N6Li2O24V6，三方空间群R，a = 13.7185(3)埃，c = 24.8899(8)埃，Z = 3。2的晶体数据：C36H80ClN6NaO25V6，三斜空间群P，a = 11.1817(5)埃，b = 12.1612(5)埃，c = 21.5979(10)埃，α = 75.8210(10)，β = 78.8270(10)，γ = 71.1400(10)，Z = 2。4的晶体数据：C36H78Cl2N6MnO24V6，单斜，空间群P2(1)，a =11.2208(5)埃，b = 21.5041(9)埃，c = 11.8126(5)，β = 111.2680，Z = 2。5的晶体数据：C36H78Cl2N6FeO24V6，单斜，空间群P2(1)，a = 11.3057(7)埃，b = 21.4372(13)埃，c = 11.8167(7)埃，β = 111.4170，Z = 2。