| Project/Area Number |
59430017
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| Research Category |
Grant-in-Aid for General Scientific Research (A)
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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 Kyoto University, Professor, 工学部, 教授 (60025814)
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| Co-Investigator(Kenkyū-buntansha) |
MIKI Sadao Kyoto University, Instructor, 工学部, 助手 (30135537)
SUGIMOTO Toyonari Kyoto University, Instructor, 工学部, 助手 (30093256)
TAMARU Yoshinao Kyoto University, Associate Professor, 工学部, 助教授 (80026319)
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| Project Period (FY) |
1984 – 1986
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| Project Status |
Completed (Fiscal Year 1986)
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| Budget Amount *help |
¥29,800,000 (Direct Cost: ¥29,800,000)
Fiscal Year 1986: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1985: ¥12,000,000 (Direct Cost: ¥12,000,000)
Fiscal Year 1984: ¥16,800,000 (Direct Cost: ¥16,800,000)
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| Keywords | Cyclic polycalicene / Polarization / Radialene / Electron donor / Norbornadiene / Photochromism / Photo-isomerization / フォトクロミズム / 高歪化合物 / シクロプロペニウムイオン / ビシクロブタン / 複素環合成 / 原子価異性 / 可逆的情報記録材料 / 導電材料 |
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| Research Abstract |
We have performed our research with the titled project for the period of 1984-1986. The following results were obtained:
1. The three cyclic polycalicenes were synthesized, and their electronic structures in the ground state were investigated on the basis of <^1H> - and <^(13)C> -NMR spectral data, and also of molecular orbital and graph theoretical calculations. In all the cases aromatic stabilization occurs, although the degree tends to decrease with an increasing number of calicene unit. The large <pi> conjugation of cyclopropenium and cyclopentadienyl ions produced by polarization of each calicene unit plays an important role on the stabilization of the total <pi> system.
2. 1,3-Dithiole[4]- and [6]-radialenes were synthesized, which have strong electron-donating ability. In particular, with TCNQ and its tetrafluoro derivative the [4]radialenes formed CT complexes, whose electrical conductivities are considerably high ( <10^(-2)> - <10^(-1)> S/cm). The thioxanthenyl[3]radialene was i
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solated as blue crystals, which can be expected as a desirable electron donor for synthetic metals, on the basis of its high planarity and expected electron-donating ability.
Norbornadienes possessing both donor and acceptor groups (DA-NBD) were synthesized. They revealed an extinction at visible region due to CT transition of electrons, and upon irradiation at the CT band they isomerized to the corresponding quadricyclanes (DA-Q) quantitatively with high quantum efficiency. Photochromic solid PMMA films doped with this new type of photochromic systems were prepared. Noteworthy is the remarkably high repetitionality of the chemical oscillations in the film.
4. New photochromic systems based on photochemical interconversion between polycyclic aromatic compounds and their valene isomers were prepared. 1,2,3-tri-t-butyl-naphthalene isoquinoline and anthracene gave their valene isomers photolytically. The valene isomers were kinetically stable, and thus, these systems were found to be typical "P Type" photochromism. Less
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