| Project/Area Number |
62470085
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | Kyoto University |
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Principal Investigator |
YOSHIDA Zen-ichi Faculty of Engineering Kyoto University, Professor, 工学部, 教授 (60025814)
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| Co-Investigator(Kenkyū-buntansha) |
MIKI Sadao Faculty of Engineering Kyoto University, Instructor, 工学部, 助手 (30135537)
SUGIMOTO Toyonari Faculty of Engineering Kyoto University, Associate Professor, 工学部, 助教授 (30093256)
TAMARU Yoshinao Faculty of Engineering Nagasaki University, Professor, 工学部, 教授 (80026319)
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| Project Period (FY) |
1987 – 1988
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| Project Status |
Completed (Fiscal Year 1988)
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| Budget Amount *help |
¥7,900,000 (Direct Cost: ¥7,900,000)
Fiscal Year 1988: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1987: ¥5,800,000 (Direct Cost: ¥5,800,000)
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| Keywords | Cyclic polycalicene / Anthraquinone / Photovalence-isomerization / Photochromism / Radialene / Electrochromism / 有機強磁性体 / 環状テトラカリセン / 分極 / 歪アントラキノン / ヘミヂュワーアントラキノン / 1、3ージチオール〔5〕ラジアレン / レドックス / 環状トリカリセン / 高歪みアントラキノン / 光化学反応 / nπ* / ππ* / 電子供与性ラジアレン / 有機電導体 |
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| Research Abstract |
We have performed our research with the titled project for the period of 1987 - 1988. The following results were obtained:
(1) The defference of electronic structure between bis(tert-butylthio) derivatives of cyclic bi-, tri-, and tetra-calicenes was investigated on the basis of ^1H- and ^<13>C-NMR, and redox potential results. It was shown that each calicene unit polarizes in almost the same degree irrespectively of the number of calicene units.
(2) Introduction of some bulky groups into electron systems, provides remarkable change in their electronic structures. Now, anthraquinones substituted with tert-butyl or trimethylsilyl groups at the 1, 2, and 3-positions, were synthesized. Under photoirradiation the anthraquinones were subjected to valence isomerization into the corresponding hemi-Dewar types of anthraquinones. This reaction is photochemically reversible and quantitaltive, thus bringing much expectation as a new type of photochromic system. Also, time-resolved spectrometric study demonstrated that the photochemical reaction proceeds via lowest excited sinlet and triglet.
(3) Since 1,3-dithiole[n]radialenes construct a novel redox system and exhibit electrochromism, they can be expected as reliable component for a new type of electrochromic material. Furthermore, the odd-numbered radialenes were shown to have a possibility of a donor component for the production of a charge-transfer (CT) complex type of prganic ferromagnet, from the investigation on the magnetic properties of tris(thioxanthen-9-ylidene)cyclopropane dication salt and CT complex salts of pentakis(1.3-benzodithiol-2-ylidene)cyclopentane with DDQ and TCNQF_4 etc.
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