Construction of gigantic molecules carrying crowded triarylphosphine as key structure
| Project/Area Number |
17310063
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Nanomaterials/Nanobioscience
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| Research Institution | Tohoku University |
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Principal Investigator |
SHIGERU Sasaki Tohoku University, Tohoku University, Garaduate School of Science, Assistant professor (90254143)
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| Project Period (FY) |
2005 – 2007
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| Project Status |
Completed (Fiscal Year 2007)
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| 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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| Keywords | triarylphosphine / quinone / oligomer / Suzuki-Miyaura coupling / intramolecular charge transfer / redox properties / mixed valence / ^31P NMR / トリアリールホズフィン / ニトロキシド / アゾベンゼン / 酸化 / 還元 / 電荷移動吸収 / 鈴木カップリング / デンドリマー / 電子スプレーイオン化 |
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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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Report
(4 results)
Research Products
(57 results)
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[Presentation] Synthesis, Structure, and Properties of Crowded Triarylphosphines Carrying Quinone Moieties2006
Author(s)
Shigeru Sasaki, Kazunobu Ogawa, Masaaki Yoshifuji, and Noboru Morita
Organizer
JSPS Core-toCore Program, Innovative Synthesis of Novel Main-Group Compounds and Its Application, Second Core-to-Core Symposium on Main Group Element Chemistry
Place of Presentation
Yayoi Auditorium, The University of Tokyo, Tokyo, Japan
Description
「研究成果報告書概要(和文)」より
Related Report
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