Construction of Photosensitive Device by Using of Hydrogen Bond-supported Metal Complex Assembly

利用氢键支撑的金属配合物组装体构建感光器件

基本信息

批准号：
15550050
负责人：
KAWATA Satoshi
金额：
$ 2.43万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2004
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550050/
关键词：
Metal Complex Assembly Hydrogen Bond Vapochromism Spin-crossover 層状化合物

项目摘要

Novel metal-complex assemblies constructed from the flexible hinge-like ligand H_2bhnq (H_2bhnq= 2,2' -bi(3-hydroxy-1,4-naphthoquinone))have been synthesized. The X-ray crystal structures of these compounds reveal that four types of architectures are accessible by variation of the metal ions. In copper(II) compounds 1-3, the chelating bhnq^<2-> ions bridge copper(II) centers to form one-dimensional zigzag chains. The chains of 1-3 are arranged by hydrogen-bonding interactions and stacking interactions to produce porous structures. Cobalt(II) and zinc(II) compounds 4 and 5 form one-dimensional helical chains. In 4 and 5, the crystal packing induces spontaneous resolution of the helical chains with chiral cavities formed perpendicular to the helices. Nickel(II) compounds 6 and 7 formcyclic tetramers. The fourth architecture, a dimer (compound 8), is obtained by the reaction of zinc(II) and bhnq^<2-> in McOH. In these compounds, changes of the dihedral angles and the metal-coordination mode of the bhnq^<2-> ion induce the structural versatility. The assemblies of the zigzag chains of the copper(II) compounds exhibit reversible vapochromic behavior. UV/V is, powder X-ray diffraction, EPR, and adsorption isotherm measurements indicate that this vapochromic behavior is based on the hinge-like flexibility of the bhnq^<2-> ion.

由柔性铰链状配体H_2bhnq（H_2bhnq = 2,2'-双（3-羟基-1,4-萘醌））构建的新型金属配合物组件已被合成。这些化合物的 X 射线晶体结构表明，通过金属离子的变化可以形成四种类型的结构。在铜(II)化合物1-3中，螯合bhnq^2-离子桥接铜(II)中心形成一维之字形链。 1-3的链通过氢键相互作用和堆积相互作用排列以产生多孔结构。钴(II)和锌(II)化合物4和5形成一维螺旋链。在4和5中，晶体堆积导致螺旋链自发拆分，并形成垂直于螺旋的手性空腔。镍(II)化合物6和7形成环状四聚体。第四种结构是二聚体（化合物8），是通过锌(II) 和bhnq^<2-> 在甲醇中反应获得的。在这些化合物中，bhnq^2-离子的二面角和金属配位模式的变化导致了结构的多功能性。铜(II)化合物的锯齿形链的组装表现出可逆的气色行为。 UV/V is、粉末X射线衍射、EPR和吸附等温线测量表明这种汽致变色行为是基于bhnq^2-离子的铰链状柔性。