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

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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.