| Project/Area Number |
10440215
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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 |
物質変換
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| Research Institution | KYOTO UNIVERSITY |
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Principal Investigator |
ITO Yoshikatsu Kyoto University, Graduate School of Engineering, Associate Professor, 工学研究科, 助教授 (20093726)
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| Project Period (FY) |
1998 – 2001
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥13,500,000 (Direct Cost: ¥13,500,000)
Fiscal Year 2001: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 2000: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 1999: ¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 1998: ¥7,600,000 (Direct Cost: ¥7,600,000)
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| Keywords | two-component crystals / cocrystals / solid-state photodimerization / diamine / dicarboxylic acid / cinnamic acid / cinnamamide / intermolecular interaction / アミン / ドーパミン / アルケン / メラニン / 固相光反応 / 光二量化反応 / 混合光二量化反応 / 多成分結晶 / 水素結合性リンカー / 超分子光化学 / 電子供与体-受容体 / 水素結合供与体-受容体 |
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| Research Abstract |
Creation of the desired photoreactivity by constructing new two-component crystals was studied The solids which we dealt with are crystalline organic salts, hydrogen-bonded cocrystals, donor-acceptor crystals, mixed crystals, and solid mixtures. The methods which we used in order to control the photochemistry of the one component in the crystal are based on manipulating a range of non-bonding intermolecular interactions in the solid state. Main results are summarized below.
1. A series of diamines were investigated to steer the photodimerization of trans-cinnamic acids and anthracenecarboxylic acids. It has been found that trans- and cis-cyclohexane-1,2-diamines or gauche 1,2-diamines are useful linkers for preparing double salts of unusual photoreactivity. By this method even the thermally unstable anthracene head-to-head dimer was obtained as a sole product.
2. Divalent metals (M = Mg, Ca, Sr, Ba, Zn) were used instead of diamines as a linker for two acid molecules. These metal-contain
… More
ing salts often crystallized together with water (and solvent) and the included solvent or water hampered the photoreactivity.
3. Solid-state photodimerization of trans-cinnamamides into unusual head-to-head dimers was achieved by using a dicarboxylic acid. Phthalic acid played the role as an intermodular linker and oxalic add as the layered host. In the former case, a pedal-like dynamic conformational change is thought to occur in the crystal prior to cycloaddition.
4. We have found (a) the photoreductive coupling reaction of the cyano group occurring in the crystallme 1:2 complex between tetracyanobenzene and benzyl cyanide and (b) the cross photo-dimerization occurring in the hydrogen-bonded 1:2 cocrystal between fumaric acid and trans-cinnamamide. A crystalline salt of tryptamme with trans-3-nitrocinnamic acid also underwent novel cross photocycloaddition. As to the generality of these reactions, however, we must establish as yet unknown protocols for fabricating crystal structures of desired photoreactivity. This goal is still a long way to go.
We are now studying the chemistry of dopamine and its derivatives. For example, dopamine forms two-component crystals with some nitro compounds. Less
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