Dynamics of Photodissociation and Rearrangement of Chemical Bonds in Solution

溶液中化学键光解离和重排的动力学

• 批准号: 02453013
• 负责人: OKADA Tadashi
• 金额: $ 3.65万
• 依托单位: Osaka 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: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-02453013/
• 关键词: photodissociation; Microscopic Diffusion; tetraarylhydrazine; heterodimer; predissociation; Picosecond Laser Spectroscopy; テトラフェニルヒドラジン; アントラセンヘテロダイマ-; 光シクロ附加; 環開裂

l. Photodissociation of Heterodimers of Anthracene and 1, 4-Dihalobebzens in SolutionWhen a heterodimer is excited in solution, a excited singlet state of anthracene and a ground state of dihalobenzene are produced from the excited singlet state of the heterodimer. We have measured the time-dependence of the fluorescence of heterodimer itself and produced anthracene as well as the time-resolved transient absorption spectra in solution by means of a picosecond laser spectroscopy.The fluorescence spectrum of anthracene observed by the excitation of heteroexcimer in glass matrix at 77K is shifted to the red about 10nm compared to that of free anthracene, which indicate that a special intermolecular conformation between anthracene and dihalobenzene may be preserved in the low temperature matrix. Dynamical shifts of anthracene fluorescence were detected at room temperature in viscous solvent, cis-decalin.2. Photodissociation of Tetraphenylhydrazine and Its Derivatives in SolutionThe slow N-N bond rupture occurring in the fluorescence state of tetraarylhydrazines has been confirmed by a picosecond time-resolved spectroscopy. The predissociation mechanism from the excited singlet (fluorescent) state to the lower lying dissociative state was proposed.

当一个杂二聚体在溶液中被激发时，由该杂二聚体的激发单重态产生了菲的激发单重态和二卤苯的基态。利用皮秒激光光谱仪测量了杂二聚体本身的荧光随时间的变化，并用皮秒激光光谱仪测量了溶液中产生的菲以及时间分辨的瞬时吸收光谱。在77K时，在玻璃基质中被异准分子激发观察到的菲的荧光光谱比游离的菲的荧光光谱红移了约10 nm，这表明在低温的基质中可能保留了菲和二卤苯之间的特殊分子间构象。结果表明：1.在室温下，菲荧光在顺式十氢呋喃的粘性溶剂中发生动态位移。四苯肼及其衍生物在溶液中的光解离四芳基肼在荧光状态下发生的缓慢N-N键断裂已被皮秒时间分辨光谱所证实。提出了从激发单重态(荧光)到下位解离态的预解离机制。

项目成果

Y.Hirata: "Direct Observation of Photodissociation of Tetraphenylhydrazine and its Derivatives in the Solution Phase: Picosecond Study of N-N Bond Rupture in the Fluorescence State" J.Phys.Chem.96. 1517-1520 (1992)

Y.Hirata：“四苯肼及其衍生物在溶液相中光解离的直接观察：荧光状态下 N-N 键断裂的皮秒研究”J.Phys.Chem.96。

T.Okada: "Photoinduced Intramolecular Charge Transfer of TICT and Related Compounds in Femtosecond-Nanosecond Time Regime" Proc.Indian Acad.Sci.(Chem.Sci.),April,1992,. (1992)

T.Okada：“飞秒-纳秒时间范围内 TICT 和相关化合物的光诱导分子内电荷转移”Proc.Indian Acad.Sci.(Chem.Sci.)，1992 年 4 月。

T. Okada, M. Maruyama, M. Ishigaki, H. Okammoto, and M. Kimura: "Picosecond Laser Photolysis Studies on the Photodissociation Process of Heterodimers of Anthracene and 1, 4-Dihalobenzenes in Solution"

T. Okada、M. Maruyama、M. Ishigaki、H. Okammoto 和 M. Kimura：“溶液中蒽和 1, 4-二卤苯异二聚体光解离过程的皮秒激光光解研究”

岡田 正: "時間分解吸収分光(psーfs)第4版実験化学講座7、分光II" 日本化学会編、丸善, 516 (1992)

冈田正：《时间分辨吸收光谱法 (PS-FS) 第 4 版实验化学课程 7，光谱学 II》，日本化学会编，丸善，516 (1992)

S.Nishikawa: "Determination of the Bimolecular Rate Constant of Photoinduced Charge Separation in the Energy Gap Region Where the Reaction is Diffusion ControlledーAnalysis of the Transient Effect in the Course of Fluorescence Quenching Reaction" Chem.Phys

S. Nishikawa：“反应扩散控制的能隙区域光致电荷分离双分子速率常数的测定——荧光猝灭反应过程中的瞬态效应分析” Chem.Phys