Synthesis of novel metal complexes exhibiting multi-stabilities and creation of molecular systems exhibiting multi-functionalities

本研究的目的是建立一种化学、物理结构和光、磁、电性质可逆变化的智能分子系统，并将其与电极表面结合，制备“分子功能器件”。对于□共轭氧化还原络合物低聚物和聚合物，我们成功地通过表面逐步配位反应自底向上合成了一维和三维低聚物络合物分子线，并首次发现了氧化还原沿着分子线传导的现象。还使用具有末端卟啉部分的这种分子线制备了光电子传导分子线。在光致变色配合物方面，我们合成了具有通过改变氧化还原态来控制记忆深度的二茂铁螺吡喃，（二茂铁基乙炔基）乙烷及其三芳基胺衍生物，其通过光异构化引起末端氧化还原部分之间的电子连通的改变，以及二茂铁基偶氮苯的自组装单层，其通过与二茂铁部分的氧化还原反应相结合，用单一绿色光源进行偶氮苯部分的可逆异构化。对于给体-受体共轭分子，我们发现1-二茂铁乙炔基蒽醌与质子发生环化反应生成吡啶盐，并随温度变化发生价态互变异构。我们还发现，1，4-双（二茂铁乙炔基）蒽醌通过吸附客体分子发生可逆的单晶-单晶结构变化。在杂金属簇合物方面，我们通过金属二硫纶与金属羰基化合物的反应，合成了几种新型的簇合物。它们具有独特的氧化还原和光学性质。

The purpose of this study is to create intelligent molecular systems where the chemical and physical structures and the optical, magnetic and electronic properties are changed reversibly and then to produce "molecular functional devices" by combining the molecular systems with electrode surface. As for □-conjugated redox complex oligomers and polymers, we have succeeded in bottom-up synthesis of one- and three-dimensional oligomer complex molecular wires by step-wise coordination reactions on the surface, and have found the phenomena of redox-conduction along the molecular wires for the first time. Photo-electron conducting molecular wires were also prepared using such molecular wires with terminal porphyrin moieties. As for photochromic complexes, we synthesized ferrocenylspiropyran with an ability to control the memory depth by changing the redox state, bis(ferrocenylethynyl)ethane and its triarylamine derivatives, which cause alteration of electronic communication between terminal redox moieties by photoisomerization, and self-assembled monolayers of ferrocenylazobenzene, which undergoes reversible isomerization of azobenzene moieties with a single green light source by combining with the redox reaction of ferrocene moiety. As for donor-acceptor conjugated molecules, we have found that 1-ferrocenylethynylanthraquinone reacts with proton to cause cyclization reaction to give a pyrilium salt, which shows valence tautomerization with temperature change. We have also found that 1,4-bis(ferrocenylethynyl)anthraquinone undergoes reversible single crystal - single crystal structural changes by absorption of guest molecules. As for heterometal cluster complexes, we synthesized several types of new cluster complexes by the reaction of metalladithiolenes with metal carbonyls. They exhibit unique redox and optical properties.