Hydrogen Bond Supported Metal Assembled Compounds of Chloranilic acid

氢键负载的氯苯甲酸金属组装化合物

基本信息

批准号：
10640541
负责人：
KAWATA Satoshi
金额：
$ 2.43万
依托单位：
Shizuoka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 1999
项目状态：
已结题

项目摘要

Design and synthesis of molecular based materials is a booming field of research in crystal engineering. Hydrogen bonding interaction is one of the active tools to construct metal organic suprastructures. In this context, usage of mixed organic ligands helps to get predictable molecular architecture having potential properties such as magnetism, conductivity and non-linear optics.Chloranilic acid is one the member of oxocarbon family provides 1D chains and 2D layers with various metal ions. We have synthesized iron assembled compound of chloranilic acid, {[Fe(CP*)ィイD22ィエD2][Fe(CA)ィイD22ィエD2(HィイD22ィエD2O)ィイD22ィエD2]}<D2n>D2 (1) (HィイD22ィエD2CA = chloranilic acid, Cp*ィイD1-ィエD1 = decamethyl cyclopentadienide) and Cu and Zn assembled compounds of chloranilic acid and tptz, {[M(CA)(tptz)(HィイD22ィエD2O)](HィイD22ィエD2O)} (tptz = 2,4,6-tris(2-pyridyl)-l,3,5,-triazine, M = CuィイD12+ィエD1 (2), ZnィイD12+ィエD1 (3). Here the crystal structures of the three compounds are described.Compound 1 consists of 2D anionic layer {[Fe(CA)ィイD22ィエD2(HィイD22ィエD2O)ィイD22ィエD2]ィイD1-ィエD1}n and [Fe(CP*)ィイD22ィエD2]ィイD1+ィエD1 guest cations. The geometry around the iron(III) ion in the layer is a distorted octahedron, where four oxygen atoms from two CAィイD12-ィエD1 and two oxygen atoms from two water molecules are coordinated (Fig. 1). The octahedral units make 2D layer by hydrogen bonding interaction, which occurs between the terminal oxygen atoms of CAィイD12-ィエD1 and the coordinated water molecules. The [Fe(CP*)ィイD22ィエD2]ィイD1+ィエD1 cations are intercalated between the layers by electrostatic interaction.Compound 2 and 3 are isomorphous and are made of CAィイD12-ィエD1 and tptz coordinated octahedral building units, which make 1D chains by hydrogen bonding interaction. Each metal ion is coordinated by two oxygen atoms from one CAィイD12-ィエD1, three nitrogen atoms from one tptz and one oxygen from a water molecule. Interstitial water molecules are included by hydrogen bonding interaction.

分子材料的设计和合成是晶体工程中一个蓬勃发展的研究领域，氢键相互作用是构建金属有机超结构的活跃工具之一，在这种背景下，混合有机配体的使用有助于获得具有潜在特性的可预测的分子结构。例如磁性、导电性和非线性光学。氯苯甲酸是含氧碳家族的成员之一，提供各种金属离子的一维链和二维层。我们合成了氯苯酸的铁组装化合物， {[Fe(CP*)D22D2][Fe(CA)D22D2(HD22D2O)D22D2]}<D2n>D2 (1) (D22D2CA = 氯苯甲酸，Cp*D1-D1 = 十甲基环戊二烯) 和 Cu 和 Zn 组装的化合物氯苯甲酸和 tptz，{[M(CA)(tptz)(HiiD22ieD2O)](HiiiD22ieD2O)} (tptz = 2,4,6-三(2-吡啶基)-l,3,5,-三嗪，M = CuD12 +D1 (2), ZnD12+D1 (3)。描述了三种化合物的晶体结构。化合物 1 由 2D 阴离子层 D1}n 和 [Fe(CP*)D22D2]D1+D1 客体阳离子组成，层中铁 (III) 离子周围的几何形状为 a。扭曲的八面体，其中两个水分子的两个氧原子中的四个氧原子配位（图1），八面体单元通过氢键相互作用形成二维层，氢键相互作用发生在CA D12-D1的末端氧原子和配位的水之间。 [Fe(CP*)D22D2]D1+D1 阳离子是化合物2和3是同晶的，由八面体结构单元组成，通过氢键相互作用形成一维链，每个金属离子由一个CA-D12-D1的两个氧原子和三个氮原子配位。一个 tptz 原子和一个水分子中的一个氧间隙水分子被氢包含。粘合相互作用。