1993 Fiscal Year Annual Research Report

新規に発見した二重結合系の光異性化とそれによる光量子作用効果の増幅

Research Project

Project/Area Number	03101004
Research Institution	University of Tsukuba
Principal Investigator	徳丸克己筑波大学, 化学系, 教授 (60011491)
Co-Investigator(Kenkyū-buntansha)	唐津孝千葉大学, 教養部, 助教授 (70214575) 土屋雅大筑波大学, 化学系, 助手 (60227436) 新井達郎筑波大学, 化学系, 講師 (50151139) 菊池修筑波大学, 化学系, 教授 (30015771)
Keywords	光片道異性化 / 二重結合 / 光量子増幅効果 / ポテンシャルエネルギー曲面 / 三重項エネルギー / 回転異性化 / 分子内水素結合 / カチオンラジカル
Research Abstract	本研究は、申請者らの発見した二重結合系の光片道異性化を展開し、二重結合系の光異性化の諸様式並びに対応するポテンシャルエネルギー曲面が分子の構造により如何に支配されるか、また、光量子の増幅効果の発現の原因を明らかにし、光異性化の全貌を総合的に把握することを目的とし、以下の結果を得た。 1)ペリレン環を置換したオレフィンは三重状態においてシス→トランス片道異性化を起こし、しかも、それが、6.6kcal mol^<-1>活性化障壁を越えて断熱的に進行することを明らかにした。 2)2-スチリルアントラセンのトランス体には単結合まわりの回転異性体が存在し、励起三重項状態において、s-transからs-cisへの一方方向のみの分子内回転を起こした。 3)1-スチリルアズレンは三重項増感によりシス→トランス片道異性化を起こした。 4)アントラセン環の2位に置換したC=N二重結合系は光照射により量子連鎖的なシス→トランス片道異性化を起こすが、これが三重項ポテンシャル曲面上で6kcal mol^<-1>の活性化障壁を越えて進むことを明らかにした。また、トランス体は単結合に関してs-cis体及びs-transとして存在し、室温では主に励起一重項で、低温では励起三重項でs-trans体からs-cis体へ変換することを明らかにした。 5)アントラセン環の9位に置換したC=N二重結合系は三重項増感により量子連鎖的なシス→トランス片道異性化を起こすが、直接光照射により両方向異性化を示すことを明らかにした。 6)キノリン環とピロール環を置換したオレフィンは光照射によりシス体とトランス体の間で両方向に異性化し、また、シス型を光励起すると分子内水素結合を介しての水素移動を起こして励起状態で互変異性化を起こした。 7)1-スチリルピレンのベンゼン環のパラ位に極性置換基を導入すると異性化を制御できることを明らかにした。 8)ビリルビンの光異性化反応に対するヒト血清アルブミンの結合部位の効果を明らかにした。 9)パルスラジオリシスによりカチオンラジカルの異性化におけるダイマーカチオンラジカルの寄与を示した。 10)三重項異性化とカチオンラジカルのシス→トランス異性化のポテンシャル曲面の計算を行ない、実験結果と定性的に一致する結果得た。

Research Products
(18 results)

All Other

All Publications (18 results)

[Publications] T.Arai: "Trans→cis one-way photoisomerization of an olefin substituted with an indole and a pyridine ring.Effect of intramolecular hydrogen bond." Chem.Lett.691-694 (1993)
[Publications] Y.Gong: "One-way photoisomerization of dienes substituted by an anthracene nucleus." Chem.Lett.753-756 (1993)
[Publications] Y.Kanna: "Photoisomerization of bilirubins and the role of intramolecular hydrogen bonds." Bull.Chem.Soc.Jpn.66. 1482-1489 (1993)
[Publications] Y.Kanna: "Effect of serum albumins from several mammals on the photoisomerization of bilirubin." Bull.Chem.Soc.Jpn.66. 1586-1588 (1993)
[Publications] B.W.Zhang: "Salt effect for accelerating charge separation from 9,10-dicyano-anthracene-stilbene exciplex in dichloromethane." Bull.Chem.Soc.Jpn.66. 1859-1862 (1993)
[Publications] Y.Kikuchi: "Effect of substituents on the equilibrium between trans and perpendicular conformers at the triplet excited state of substituted styrylpyrenes." Chem.Lett.833-836 (1993)
[Publications] Y.Kuriyama: "Mechanism for isomerization of cis-stilbene via its radical cation as investigated by pulse radiolysis.A possible role of a dimeric radical cation as an intermediate." Bull.Chem.Soc.Jpn.66. 1852-1855 (1993)
[Publications] T.Oshiyama: "Multi-reference CI calculation of potential energy curves for cis-trans isoemrization of stilbene cation radical." Bull Chem.Soc.Jpn.66. 1622-1626 (1993)
[Publications] T.Arai: "Photoisomerization of bilirubin." “Recent Advances in Photosciences".Proceedings of International Symposium on Photochemistry,Photobiology and Photomedicine,Sep.13-16,1992,ed.by M.Yoon,P-S.Song. 28-34 (1993)
[Publications] K.Segawa: "Ab initio triplet potential energy curves of methyl-substituted arylethylenes along the double bond twisting." Bull Chem.Soc.Jpn.66. 2754-2757 (1993)
[Publications] Y.Kikuchi: "Effect of acetonitrile completely suppressing trans-to-cis photoisomerization of styrylpyrene substituted with a nitro group." Chem.Lett.1811-1812 (1993)
[Publications] T.Arai: "One-way Z→E isomerization around the double bond of N-methoxy-1-(2-anthryl)ethanimine in the excited triplet state.Direct observation of one-way isomerization from Z triplet to E triplet of the C=N bond." Chem.Phys.Lett.212. 597-603 (1993)
[Publications] T.Arai: "Potential energy surfaces of a one-way photoisomerizing olefin studied by photoacoustic calorimetry and X-ray crystallography." J.Photochem.Photobiol.A:Chem.75. 85-90 (1993)
[Publications] T.Karatsu: "Photochemical“across-a-ridge"Z-E isomerization of (ethenyl-2-d)-anthracenes in the triplet state." J.Phys.Chem.98. 508-512 (1994)
[Publications] T.Arai: "The effect of substitution of 3-perylenyl group,an aromatic nucleus with a very low triplet energy,on photochemical isomerization of the unsaturated bond.Direct observation of triplet state isomerization of a styrene derivative." Chem.Lett.205-208 (1994)
[Publications] T.Karatsu: "Rotational isomerization of trans-2-styrylanthracene between (s)-trans and (s)-cis rotamers in the excited state.Investigation of its sterically restriced model compounds." Chem.Lett.381-384 (1994)
[Publications] T.Arai: "A novel photoinduced hydrogen atom transfer through intramolecular hydrogen bonding coupled with cis-trans isomerization in cis-1-(2-pyrrolyl)-2-(2-quinolyl)ethene." J.Am.Chem.Soc.(in press.). (1994)
[Publications] T.Karatsu: "Photochemical cis to trans one-way isomerization styrylazulenes on their triplet excited states.Examination of ethylenes with non-benzenoid substituents of low triplet energies." Bull.Chem.Soc.Jpn.(in press.). (1994)

1993 Fiscal Year Annual Research Report

新規に発見した二重結合系の光異性化とそれによる光量子作用効果の増幅

Principal Investigator

徳丸 克己 筑波大学, 化学系, 教授 (60011491)

Research Products

[Publications] T.Arai: "Trans→cis one-way photoisomerization of an olefin substituted with an indole and a pyridine ring.Effect of intramolecular hydrogen bond." Chem.Lett.691-694 (1993)

[Publications] Y.Gong: "One-way photoisomerization of dienes substituted by an anthracene nucleus." Chem.Lett.753-756 (1993)

[Publications] Y.Kanna: "Photoisomerization of bilirubins and the role of intramolecular hydrogen bonds." Bull.Chem.Soc.Jpn.66. 1482-1489 (1993)

[Publications] Y.Kanna: "Effect of serum albumins from several mammals on the photoisomerization of bilirubin." Bull.Chem.Soc.Jpn.66. 1586-1588 (1993)

[Publications] B.W.Zhang: "Salt effect for accelerating charge separation from 9,10-dicyano-anthracene-stilbene exciplex in dichloromethane." Bull.Chem.Soc.Jpn.66. 1859-1862 (1993)

[Publications] Y.Kikuchi: "Effect of substituents on the equilibrium between trans and perpendicular conformers at the triplet excited state of substituted styrylpyrenes." Chem.Lett.833-836 (1993)

[Publications] Y.Kuriyama: "Mechanism for isomerization of cis-stilbene via its radical cation as investigated by pulse radiolysis.A possible role of a dimeric radical cation as an intermediate." Bull.Chem.Soc.Jpn.66. 1852-1855 (1993)

[Publications] T.Oshiyama: "Multi-reference CI calculation of potential energy curves for cis-trans isoemrization of stilbene cation radical." Bull Chem.Soc.Jpn.66. 1622-1626 (1993)

[Publications] T.Arai: "Photoisomerization of bilirubin." “Recent Advances in Photosciences".Proceedings of International Symposium on Photochemistry,Photobiology and Photomedicine,Sep.13-16,1992,ed.by M.Yoon,P-S.Song. 28-34 (1993)

[Publications] K.Segawa: "Ab initio triplet potential energy curves of methyl-substituted arylethylenes along the double bond twisting." Bull Chem.Soc.Jpn.66. 2754-2757 (1993)

[Publications] Y.Kikuchi: "Effect of acetonitrile completely suppressing trans-to-cis photoisomerization of styrylpyrene substituted with a nitro group." Chem.Lett.1811-1812 (1993)

[Publications] T.Arai: "One-way Z→E isomerization around the double bond of N-methoxy-1-(2-anthryl)ethanimine in the excited triplet state.Direct observation of one-way isomerization from Z triplet to E triplet of the C=N bond." Chem.Phys.Lett.212. 597-603 (1993)

[Publications] T.Arai: "Potential energy surfaces of a one-way photoisomerizing olefin studied by photoacoustic calorimetry and X-ray crystallography." J.Photochem.Photobiol.A:Chem.75. 85-90 (1993)

[Publications] T.Karatsu: "Photochemical“across-a-ridge"Z-E isomerization of (ethenyl-2-d)-anthracenes in the triplet state." J.Phys.Chem.98. 508-512 (1994)

[Publications] T.Arai: "The effect of substitution of 3-perylenyl group,an aromatic nucleus with a very low triplet energy,on photochemical isomerization of the unsaturated bond.Direct observation of triplet state isomerization of a styrene derivative." Chem.Lett.205-208 (1994)

[Publications] T.Karatsu: "Rotational isomerization of trans-2-styrylanthracene between (s)-trans and (s)-cis rotamers in the excited state.Investigation of its sterically restriced model compounds." Chem.Lett.381-384 (1994)

[Publications] T.Arai: "A novel photoinduced hydrogen atom transfer through intramolecular hydrogen bonding coupled with cis-trans isomerization in cis-1-(2-pyrrolyl)-2-(2-quinolyl)ethene." J.Am.Chem.Soc.(in press.). (1994)

[Publications] T.Karatsu: "Photochemical cis to trans one-way isomerization styrylazulenes on their triplet excited states.Examination of ethylenes with non-benzenoid substituents of low triplet energies." Bull.Chem.Soc.Jpn.(in press.). (1994)

徳丸克己筑波大学, 化学系, 教授 (60011491)