Effects of Magnetic Fields on the Relaxation Processes of Photoexcited Oordination Compounds.

磁场对光激发配位化合物弛豫过程的影响。

• 批准号: 61470043
• 负责人: KAIZU Youkoh
• 金额: $ 3.52万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1986
• 资助国家: 日本
• 起止时间: 1986 至 1987
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-61470043/
• 关键词: Porphyrin hybrid dimer; Intramolecular energy transfer; TT annihilation; T-T吸収; エネルギー移動

Energy transfer from the excited triplet (trip-doublet and trip-quartet) state of copper porphyrin to the lowest excited triplet state of its free-base partner was detected by measurements of T-T transient absorption of a -(CH_2)_3- covalently linked porphyrin dimer. The excited dimer with free-base in the excited singlet is partly quenched by the copper counterpart. Oh the other p hand, the excited dimer with copper orphyrin in the trip-multiplet state is dissipated not only by the bast electronic relaxation within the copper porphyrin but also the intramolecular energy transfer to the free-base partner.The S_1 and S_2 delayed fluorescences were observed at om temperature with some diamagnetic metalloterraphenylporphins. The intensities and the decay-reat constants of the delayed fluorescences decreased in the presence of an external magnetic field. The same magnetic effects were observed on the S_1 and S_2 delayed fluorescences. These uesults indicate that highly energetic states (S_n, n<greater than or equal> is created by TT annihilation and give rise to the repopulation of S_1 and s_2 states.

通过对a-(CH2)3-共价连接的卟啉二聚体的T-T暂态吸收的测量，发现了铜卟啉的激发三重态(Trip-Doublet和Trip-Quartet)向其自由碱配对的最低激发三重态的能量转移。激发态中含有游离碱的激发态二聚体被铜激发态部分猝灭。另一方面，与铜或卟啉处于Trip多重态的激发二聚体不仅通过铜卟啉内部的电子弛豫耗散，而且还通过分子内能量转移到自由碱配位而耗散。在常温下观察到S_1和S_2与一些抗磁性的金属四苯基卟啉的延迟荧光。在外加磁场的作用下，延迟荧光的强度和衰变常数减小。在S_1和S_2的延迟荧光中观察到了相同的磁效应。这些结果表明，高能态(S n，n&lt；大于或等于&gt；)是由于TT湮灭而产生的，并导致了S_1和S_2态的再布居。

项目成果

M. Asano;O. Ohno and Y. Kaizu: Photochemistry and Photophysics of Coordination Compounds(Ed. H. Yersin and A. Vogler). 291-294 (1987)

M.浅野；O.

O. Ohno;Y. Ogasawara;M. Asano;Y. Kajii;Y. Kaizu;K. Obi and H. Kobayashi: J. Phys. Chem.91. 4269-4273 (1987)

O.大野；Y.

O. Ohno, Y. Ogasawara, M. Asano, Y. Kajii, Y. Kaizu, K. Obi, and H. Kobayashi: "Triplet-Triplet Energy Transfer in a Copper(II) Porphyrin-Free-Base Porphyrin Dimer." J.Phys.Chem.91. 4269-4273 (1987)

O. Ohno、Y. Ogasawara、M. Asano、Y. Kajii、Y. Kaizu、K. Obi 和 H. Kobayashi：“铜（II）无卟啉基卟啉二聚体中的三重态-三重态能量转移”。

小笠原,浅野,大野,海津,小林,梶井,小尾: 分子構造総合討論会'86. 482 (1986)

小笠原、浅野、大野、海津、小林、梶井、奥比：分子结构综合讨论组86（1986）。

浅野,大野,海津,小林: 錯塩化学討論会'86. 389 (1986)

Asano、Ohno、Kaizu、Kobayashi：复杂盐化学研讨会86（1986）。