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

• 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
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10640541/
• 关键词: Metal Assembled Complex; Chloranilic Acid; Hydrogen Bond; Iron; Layer Compound; Chain Compound; 集積体; インターカレーション; 層間化合物; 多重機能

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.

分子基材料的设计与合成是晶体工程中一个新兴的研究领域。氢键相互作用是构建金属有机上层结构的有效工具之一。在这种情况下，混合有机配体的使用有助于获得具有磁性、导电性和非线性光学等潜在性质的可预测的分子结构。氯苯酸是氧碳族的一员，具有一维链和二维层的各种金属离子。我们合成铁组装复合氯冉酸,{(Fe (CP)ィイD22摊位ィエD2) (Fe (CA)ィイD22摊位ィエD2 (HィイD22摊位ィエD2O)ィイD22摊位ィエD2)} < D2n > D2 (1) (HィイD22摊位ィエD2CA =氯冉酸,CP *ィイD1 -ィエD1 = decamethyl cyclopentadienide)和铜和锌化合物的氯冉酸和tptz组装,{[M (CA) (tptz) (HィイD22摊位ィエD2O)] (HィイD22摊位ィエD2O)} (tptz = 2, 4, 6-tris (2-pyridyl) - l, 3, 5,三嗪,M =铜ィイD12 +ィエD1(2),锌ィイD12 +ィエD1(3)。这里描述了这三种化合物的晶体结构。化合物1的2 d阴离子层{(Fe (CA)ィイD22摊位ィエD2 (HィイD22摊位ィエD2O)ィイD22摊位ィエD2)ィイD1 -ィエD1} n和(Fe (CP)ィイD22摊位ィエD2)ィイD1 +ィエD1客人阳离子。层中铁（III）离子周围的几何形状是一个扭曲的八面体，其中来自两个CA的四个氧原子和来自两个水分子的两个氧原子是配位的（图1）。八面体单元通过CA的末端氧原子与配位水分子之间的氢键相互作用形成二维层。(Fe (CP)ィイD22摊位ィエD2)ィイD1 +ィエD1阳离子在层之间插入通过静电相互作用。化合物2和3是同形的，由CA γ γ γ γ - γ γ γ - γ γ和tptz配位八面体构建单元组成，通过氢键相互作用形成一维链。每个金属离子由来自CA的两个氧原子、来自tptz的三个氮原子和来自水分子的一个氧原子配位。间隙水分子是由氢键相互作用形成的。

项目成果

S.Kawata: "Mixed Ligand Copper(II)Coordination Poymers Constructed by Cu-bpm-Cu Dimer Unit(bpm=2,2'-bipyrimidine)as a Building Block"Inorganica Chimica Acta. 283. 80-90 (1998)

S.Kawata：“以 Cu-bpm-Cu 二聚体单元（bpm=2,2-联嘧啶）为结构单元构建的混合配体铜 (II) 配位聚合物”Inorganica Chimica Acta。

S. Kawata: "Mixed Ligand Copper(II) Coordination Polymers Constructed by Cu-bpm-Cu Dimer Unit (bpm = 2,2'- bipyrimidine) as a Building Block. Crystal Structures and Magnetic Properties of {[Cu(bpm)(SOィイD24ィエD2)](HィイD22ィエD2)}ィイD2nィエD2, [Cu(bpm)ィイD21.5ィエD2(

S. Kawata：“以 Cu-bpm-Cu 二聚体单元 (bpm = 2,2-联嘧啶) 作为结构单元构建的混合配体铜 (II) 配位聚合物。{[Cu(bpm)( SO D24 D2)](H D22 D2)} D2n D2, [Cu(bpm) D21.5 D2(

M.K.Kabir: "Crystal Structure and Magnetic Property of Cobalt Assembled Compoud,{[Co(CA)(bipym)](H2O)2}n(H2CA=chloranilic acid,bipym=2,2'-bipyrimidine)"Mol. Cryst.Liq. Cryst.. in press. (2000)

M.K.Kabir：“钴组装化合物的晶体结构和磁性，{[Co(CA)(bipym)](H2O)2}n(H2CA=氯苯甲酸，bipym=2,2-联嘧啶)”Mol。

M.K.Kabir: "Novel Intercalation Structures Constructed From Iron-Chloranilate Compounds"Coord.Chem.Rev.. (in press). (2000)

M.K.Kabir：“由氯苯酸铁化合物构建的新型插层结构”Coord.Chem.Rev..（出版中）。

M.Katada, S.Kawata et al.: "Synthsis and 151Eu-and 57Fe-Mossbauer spectroscopic studies of new europium-iron complexes" Journal of Radioanalytical and Nuclear Chemistry. 239-2. 227-232 (1999)

M.Katada、S.Kawata 等人：“新型铕铁配合物的合成和 151Eu-和 57Fe-穆斯堡尔光谱研究”《放射分析与核化学杂志》。