| Budget Amount *help |
¥14,370,000 (Direct Cost: ¥13,800,000、Indirect Cost: ¥570,000)
Fiscal Year 2007: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Fiscal Year 2006: ¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 2005: ¥10,000,000 (Direct Cost: ¥10,000,000)
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| Research Abstract |
Linear and dendritic crowded triarylphosphine-quinone oligomers (Mw ca. 3500), carrying 2,5-diaryl-1,4-benzoquinone or 1,4-naphthoquinone as a quinone moiety, were synthesized by using Suzuki-Miyaura coupling as key reaction, and relation of intramolecular charge transfer and redox properties was investigated. The oligomers were isolated as purple to blue stable solid and the corresponding intramolecular charge transfer absorption red-shifted as the difference between oxidation potential of phosphine moieties and reduction potential of quinone moieties decreased. The structure of the oligomers was strongly supported by ESI-MS and 31P NMR spectra, which reflect distribution of diastereomers arising from helicity of the propellers composed of three aromtic rings on the phosphorus atom. Introduction of a phenylene spacer between triarylphosphine and quinone and employment of naphthoquinones as quinone moieties lead to disappearance of the charge transfer band and protonation on the phosphorus works as reversible switching of the charge transfer. In addition to construction of the gigantic triarylphosphine-quinone oligomers, fundamental research on crowded triarylphosphine and some model systems were carried out. Redox properties of the crowded triarylphosphines carrying ferrocenes, triarylamines, or nitroxides, mixed valency of the crowded triarylphosphine analog of TPD, or the diaminobiphenyl known as a hole transport material for electroluminescence devices, and magnetic properties of a cation radical of the crowded triarylphosphine were revealed. Originated from exploratory research on development of inherent function of heavier main group elements by controlling flexible structure and electronic state, we constructed model systems comparable to well-known functional molecules and developed novel highly-functional gigantic molecules.
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