Metal-assembled Complexes -Chemisty Based on Inorganic-Organic Hybrid Electronic Structures-

这个优先领域的目的是通过合理的方法和理论研究的支持，设计金属组装配合物和重要的下一代材料，这些材料具有由光、电荷或自旋诱导的金属配合物的典型现象。该项目由多达119名成员在四年的时间里完成。下面提到了一些显著的结果。a)分子磁体，包括在结构确定的配合物中具有最高临界温度（T_c = 71 K）的铁磁体和作为单分子磁体的四铁（II）立方烷配合物；b)功能化配合物，如比沸石吸收更多甲烷气体的三维多孔固体和具有三阶非线性光学性质的卤化物桥接伪1D链配合物；c)超分子配合物，包括纳米级铂链配合物，更多的缔合和解离反应是由溶剂和温度控制的；d)分子基导体，包括已知的第一个单组分分子超导体和同时具有铁磁性和金属基导电性的金属配合物。新现象的发现：a)测定金属配合物红外光谱中观察到的峰聚结的快速电子转移率；b)各种光致相变现象，包括光致自旋相变和光致电荷相变；c)电荷转移引起的一种新型相变的确定。金属组装方法和多功能化的发展：a)通过光子或质子反应实现金属配合物在混合价态的功能化；b)金属配合物在固体和纳米颗粒表面或界面上的组装。理论计算：发展了一种新的混合DFT （HDFT）方法，该方法适用于金属配合物的理论计算。少

The purpose of this priority area was to design, through rational methods and supported by theoretical studies, metal-assembled complexes and important next generation materials with phenomena typical of metal complexes induced by light, charge or spin. The project was carried out by as many as 119 members over a period of four years. Some of the remarkable results are mentioned below.1. Creation of novel compounds which show interesting properties and functionalities : a) Molecular magnets including a ferrimagnet which has the highest critical temperature (T_c = 71 K) among the structurally determined complexes and a tetrairon(II) cubane complex which acts as a single molecule magnet ; b) Functionalized complexes such as a 3D porpous solid which can absorb a higher amount of methane gas than zeolites and a halide-bridged pseudo 1D chain complexes exhibiting third order nonlinear optical properties ; c) Supramolecular complexes including a nano-sized platinum chain complex of which the … More association and dissociation reactions are controllable by solvent and temperature ; d) Molecular based conductors including the first known single-component molecular superconductors and metal complexes having both ferromagnetism and metal-based conductivity.2. Discovery of novel phenomena : a) Determination of the rate of rapid electron transfer from observed peak coalescence in the infrared spectrum of a metal complex ; b) Various photo-induced phase transition phenomena including a photo-induced spin transition and a photo-induced charge transition ; c) Determination of a new type of phase transision induced by charge transfer.3. Development of metal-assembling methods and multi-functionalization : a) Functionalization of metal complexes in a mixed valence state via photon or proton response ; b) Assembly of metal complexes on the surface of solids and nano-particles, or on an interface.4. Theoretical calculation : Development of a novel hybrid DFT (HDFT) method which is effective for theoretical calculations involving metal complexes. Less