以钴配合物为模板的零维钒硼磷酸盐[Co(en)(3)](2)[V(3)P(3)BO(19)][H(2)PO(4)].4H(2)O和一维钒氧化物[Co(en)(3)][V(3)O(9)].H(2)O以及[Co(dien)(2)][V(3)O(9)].H(2)O的合成与结构表征：配合物与无机网络的协同组装

Synthesis and structural characterization of 0D vanadium borophosphate [Co(en)(3)](2)[V(3)P(3)BO(19)][H(2)PO(4)].4H(2)O and 1D vanadium oxides [Co(en)(3)][V(3)O(9)].H(2)O and [Co(dien)(2)][V(3)O(9)].H(2)O templated by cobalt complexes: cooperative organization of the complexes and the inorganic networks.

作者信息

Wang Yu, Yu Jihong, Pan Qinhe, Du Yu, Zou Yongchun, Xu Ruren

机构信息

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023, People's Republic of China.

出版信息

Inorg Chem. 2004 Jan 26;43(2):559-65. doi: 10.1021/ic034241u.

DOI:10.1021/ic034241u

PMID:14731017

Abstract

A 0D vanadium borophosphate Co(en)(3)[V(3)P(3)BO(19)][H(2)PO(4)].4H(2)O (1) and two 1D vanadium oxides [Co(en)(3)][V(3)O(9)].H(2)O (2) and [Co(dien)(2)][V(3)O(9)].H(2)O (3) have been synthesized hydrothermally from the reaction mixture of V(2)O(5)-H(3)PO(4)-H(3)BO(3)-CoCl(2)-R-H(2)O at 110 degrees C (R: en or dien). The complex cations Co(en)(3)(3+) and Co(dien)(2)(3+) are cooperatively organized in the reaction medium to play a structure-directing role in the formation of the inorganic clusters and chains. The structures are determined by single-crystal X-ray diffraction analysis and further characterized by X-ray powder diffraction, ICP, and TG analyses. The structure of 1 contains isolated V(3)P(3)BO(19)(-) cluster anions, H(2)PO(4)(-) anions, racemic Co(en)(3)(3+) cations, and H(2)O molecules, which form a complex H-bond network. 2 and 3 both contain chains of corner-sharing VO(4) tetrahedra running along the 2(1) screw axis. The complex cations located in the interchain region interact with the chains through H-bonds. 2 is crystallized in an enantiomorphic space group and only one enantiomer of Co(en)(3)(3+) is involved in the structure. Crystal data: 1, monoclinic, C2/c, a = 32.8492(14) A, b = 11.9601(3) A, c = 22.6001(7) A, beta = 108.9630(8) degrees, Z = 8; 2, orthorhombic, P2(1)2(1)2(1), a = 8.1587(16) A, b = 12.675(3) A, c = 18.046(4) A, Z = 4; 3, monoclinic, P2(1)/c, a = 16.1663(10) A, b = 8.7028(3) A, c = 13.9773(5) A, beta = 103.1340(18) degrees, Z = 4.

摘要

通过在110℃下由V₂O₅ - H₃PO₄ - H₃BO₃ - CoCl₂ - R - H₂O（R：乙二胺或二乙烯三胺）的反应混合物水热合成了一种零维钒硼磷酸盐[Co(en)₃]₂[V₃P₃BO₁₉][H₂PO₄]·4H₂O（1）以及两种一维钒氧化物[Co(en)₃][V₃O₉]·H₂O（2）和[Co(dien)₂][V₃O₉]·H₂O（3）。配合物阳离子Co(en)₃³⁺和Co(dien)₂³⁺在反应介质中协同组装，在无机簇和链的形成中起结构导向作用。通过单晶X射线衍射分析确定结构，并通过X射线粉末衍射、电感耦合等离子体质谱和热重分析进一步表征。1的结构包含孤立的[V₃P₃BO₁₉]⁵⁻簇阴离子、H₂PO₄⁻阴离子、外消旋Co(en)₃³⁺阳离子和H₂O分子，它们形成复杂的氢键网络。2和3都包含沿2₁螺旋轴延伸的共角VO₄四面体链。位于链间区域的配合物阳离子通过氢键与链相互作用。2结晶于对映空间群，且结构中仅涉及Co(en)₃³⁺的一种对映体。晶体数据：1，单斜晶系，C2/c，a = 32.8492(14) Å，b = 11.9601(3) Å，c = 22.6001(7) Å，β = 108.9630(8)°，Z = 8；2，正交晶系，P2₁2₁2₁，a = 8.1587(16) Å，b = 12.675(3) Å，c = 18.046(4) Å，Z = 4；3，单斜晶系，P2₁/c，a = 16. = 16.1663(10) Å，b = 8.7028(3) Å，c = 13.9773(5) Å，β = 103.1340(18)°，Z = 4。