Design of Novel Inorganic-Organic Hybrid Materials Based on Iron-Chloranilate Mononuclear Complexes : Characteristics of Hydrogen Bond-Supported Layers toward the Intercalation of Guest Molecules

分子基材料的设计与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。氯苯酸是氧碳家族的成员之一，它提供了一维链和二维层与各种金属离子。合成了氯苯酸铁插层化合物{[G][Fe(CA)2(H2O)2]}n(H_2CA=氯苯酸，G-=客体阳离子)。所得化合物由二维阴离子层{[Fe(CA)2(H2O)2]-n和客体阳离子组成。该层中铁(III)离子周围的几何结构为扭曲的八面体，其中来自两个Ca2-的四个氧原子和来自两个水分子的两个氧原子是配位的。八面体单元通过氢键作用形成2D层，氢键作用发生在Ca2-的末端氧原子和配位的水分子之间。客体阳离子通过静电相互作用和氢键相互作用嵌入到两层之间。此外，氢键相互作用增加了体系的维度，从而提供了晶体结构的结构变化。进一步的工作将涉及到具有潜在功能的离子，如导电和/或光敏化性能，以进一步研究这一新的功能包合物材料的合成策略。

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 intercalation compounds of chloranilic acid, {[G][Fe(CA)2(H2O)2]}n (H2CA = chloranilic acid, G- = guest cations). The obtained compounds consist of 2D anionic layer {[Fe(CA)2(H2O)2]-}n and guest cations. The geometry around the iron (III) ion in the layer is a distorted octahedron, where four oxygen atoms from two CA2- and two oxygen atoms from two water molecules are coordinated. The octahedral units make 2D layer by hydrogen bonding interaction, which occurs between the terminal oxygen atoms of CA2- and the coordinated water molecules. The guest cations are intercalated between the layers by electrostatic interaction and hydrogen bonding interaction. In addition, the hydrogen bonding interaction increases the dimensionality of the system and thus provides structural varieties in the crystal structure. Further work will involve the ions which have potential functions such as conducting and/or photosensitized properties to further investigate this new synthesizing strategy for functional inclusion materials.