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

这一优先领域的目的是通过合理的方法并在理论研究的支持下，设计金属组装络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络合物的典型现象。该项目由多达119名成员在四年期间实施。下面将介绍一些显著的成果。产生显示出令人感兴趣的性质和功能的新型化合物：a）分子磁体，包括具有最高临界温度的亚铁磁体（T_c = 71 K）和作为单分子磁体的四铁（II）立方烷配合物; B）官能化的复合物，例如3D多孔固体，其可以吸收比沸石和卤化物更高量的甲烷气体。显示三阶非线性光学性质的桥接的伪1D链络合物; c）包括纳米尺寸的铂链络合物的超分子络合物， ...更多信息 缔合和解离反应可通过溶剂和温度控制; d）基于分子的导体，包括第一种已知的单组分分子超导体和具有铁磁性和基于金属的导电性的金属络合物。发现新现象：a）从金属络合物红外光谱中观察到的峰聚结确定快速电子转移速率; B）各种光诱导相变现象，包括光诱导自旋跃迁和光诱导电荷跃迁; c）确定由电荷转移诱导的新型相变。金属组装方法的发展和多功能化：a）通过光子或质子响应使金属配合物在混合价态下功能化; 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：开发了一种新的混合DFT（HDFT）方法，该方法对涉及金属络合物的理论计算有效。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