STUDY ON SPECIFIC INTERACTION AND PHOTOFUNCTIONALITY OF STABLE RADICALS FORMED BY PHOTOINDUCED ELECTRON TRANSFER REACTION

光致电子转移反应形成的稳定自由基的特异性相互作用和光功能研究

• 批准号: 05453118
• 负责人: NAGAMURA Toshihiko
• 金额: $ 4.48万
• 依托单位: SHIZUOKA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05453118/
• 关键词: Ion-pair charge-transfer complex; Photoinduced electron transfer reaction; Radicals; Charge-resonance spectrum; Styrylpyridinium; Molecular interaction; ESR; Photochromism; スチリルビリジニウム

1) Tetraphenyl salts of styrylpyridinium ions with strong electron-withdrawing groups such as nitro and dicyanovinyl groups were prepared.They formed ion-pair charge-transfer (IPCT) complexes in less polar organic solvents like 1,2-dimethoxyethane (DME).Upon excitation of an IPCT band in degassed conditions, electron transfer reaction occurred resulting in the formation of styrylpyridinyl radical with an absorption spectrum in the visible region. At the same time a broad absorption spectrum was observed in the near infrared region, which was assigned to the charge-resonance (CR) band due to the electronic interaction between a photogenerated styrylpyridinyl radical with a parent styrylpyridinium cation. The CR-band spectrum depended on the substituents and the stabilization energy was slightly higher in nitro-derivative than dicyanavinyl-derivative.2) The Electron Spin Resonance (ESR) spectrum of photoinduced radicals in dicyanovinyl-derivative was a broad singlet due to exchange broad … More ening. Hyperfine structure appeared upon mixing it with unirradiated DME solution of dicyanovinyl-derivateve, which was assigned to dimer radical cations formed by interaction of photogenerated styrylpyridinyl radicals with parent styrylpyridinium cations.3) Kinetic studies were made on these salts using a nano-second (ns) pulsed laser. The CR-band absorption rose within a ns pulse in a similar manner as the visible absorption of styrylpyridinyl radicals, strongly suggested diffusionlness formation of dimer radical cations.4) A mixture of amphipathic nitrostyrylpyridinium tetraphenylborate and arachidic acid showed a solid condensed phase at the air-water interface. Y-type Langmuir-Blodgett films were deposited on a quartz plate with deposition ratio of unity. Microcrystalline films were also prepared by evaporation. Photoexcitation of these solid films at the same condition as in solutions caused some spectral chantes. It was, however, not possible to observe the formation of styrylpyridinyl radicals and dimer radical cations in these solid films. Less

1)合成了苯乙烯基吡啶离子的四苯基盐，它们在极性较弱的有机溶剂如硝基，2-二甲氧基乙烷（DME）中形成离子对电荷转移（IPCT）络合物，在脱气条件下激发IPCT带，发生电子转移反应，形成苯乙烯基吡啶自由基，其吸收光谱在可见光区。同时在近红外区域观察到宽的吸收光谱，这被分配到电荷共振（CR）带，由于光生苯乙烯基吡啶基自由基与母体苯乙烯基吡啶阳离子之间的电子相互作用。2）二氰基乙烯基衍生物的光诱导自由基的电子自旋共振（ESR）谱是一个较宽的单重态，这是由于二氰基乙烯基衍生物的交换宽导致的 ...更多信息 恩。将其与未辐照的二氰基乙烯基衍生物的DME溶液混合后出现超精细结构，归属于光生苯乙烯基吡啶自由基与母体苯乙烯基吡啶阳离子相互作用形成的二聚体自由基阳离子。3）利用纳秒脉冲激光对这些盐进行了动力学研究。CR带吸收在纳秒脉冲内以与苯乙烯基吡啶基自由基的可见吸收相似的方式上升，强烈地表明二聚体自由基阳离子的扩散形成。4）两亲性硝基苯乙烯基吡啶四苯硼酸盐和花生酸的混合物在空气-水界面处显示出固态凝聚相。Y型LB膜是在石英板上沉积的，沉积比为1。微晶薄膜也通过蒸发制备。在与溶液相同的条件下，这些固体薄膜的光激发引起了一些光谱变化。然而，不可能观察到在这些固体膜中形成苯乙烯基吡啶基自由基和二聚体自由基阳离子。少

项目成果

T.Nagamura, A.Tanaka, H.Kawai and H.Sakaguchi: "First charge resonance band observed by steady photolysis at room temperature in solution" J.Chem.Soc., Chem.Commun. No.7. 599-601 (1993)

T.Nagamura、A.Tanaka、H.Kawai 和 H.Sakaguchi：“通过室温溶液中稳定光解观察到的第一个电荷共振带”J.Chem.Soc.、Chem.Commun。

T.Nagamura, H.Sakaguchi, T.Ito, and S.Muta: "Ultrafast color changes in organic thin films based on photoinduced electron transfer reactions" Mol.Cryst.Liq.Cryst.247. 39-48 (1994)

T.Nagamura、H.Sakaguchi、T.Ito 和 S.Muta：“基于光诱导电子转移反应的有机薄膜中的超快颜色变化”Mol.Cryst.Liq.Cryst.247。

T.Nagamura, H.Kawai, T.Ichihara, and H.Sakaguchi: "Photoinduced electron transfer and charge resonance band in ion-pair charge-transfer complexes of styrylpyridinium tetraphenylborate" Synth.Metals. (1n press.).

T.Nagamura、H.Kawai、T.Ichihara 和 H.Sakaguchi：“苯乙烯基吡啶四苯基硼酸离子对电荷转移复合物中的光诱导电子转移和电荷共振带”Synth.Metals。

Hideki Kawai: "Spcific interaction of 4-nitrostyrylpyridinium ions upon photoexcitation in solutions" Molecular Crystals and Liquid Crystals. (in press).

Hideki Kawai：“溶液中光激发时 4-硝基苯乙烯基吡啶鎓离子的特定相互作用”分子晶体和液晶。

Toshihiko Nagamura: "Photoinduced electron transfer andcharge resonance band in ion-pair charge-transfer complexes of styrylpyridinium tetraphenylborate." Synthetic Metals. (in press).

Toshihiko Nagamura：“苯乙烯基吡啶四苯基硼酸离子对电荷转移复合物中的光诱导电子转移和电荷共振带。”