Femtosecond Dynamics and Phase Relaxation of Electron Transfer Reaction in Double Metal Complex Crystals

双金属配合物晶体中电子转移反应的飞秒动力学和相弛豫

• 批准号: 09640605
• 负责人: IKEDA Noriaki
• 金额: $ 1.92万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640605/
• 关键词: Femtosecond; Electron Transfer; Double Metal Complex; Crystal; Energy Transfer; Cavity-Dumper; ルテニウム錯体

For the tilted study, a femtosecond cavity-dumped Ti : Sapphire laser has been constructed for the first time in Japan. We have succeeded to increase a pulse energy to 10 times (35 fs, 20 nJ/pulse) with variable repetition rates(10 kHz-76 MHz) in a diffraction efficiency (40-60%). Although we have tried to measure phase relaxation signals in pump-probe measurements of double metal complex crystals and thin crystal films of photo-conducting materials such as oxotitanylphthalocyanine, we could not succeed yet to get any information of phase relaxation in pump-probe measurements at this moment. This is due to a bad s/n ratio in pump-probe measurement of present our system and some thermal problems in neat crystals. We are trying to apply this method to diluted solid systems.Energy transfer reactions in guest-doped crystals have also been investigated by means of time-correlated photon-counting consists of this laser system. In the case of highly doped Os^<2+> : [Ru(bpy)_3](PF_6)_2 crystal, the host emission decay of ^3CT(Ru) was non-exponential. The decay is ascribed to the various rate constants of energy transfer depending on the excited host-guest distances, which are changed as a result of excitation migration through the host molecules. By a stochastic simulation, rates are determined to be 1.2 x 10^<10> s^<-1> for the closest Os(II) and 3 x 10^8 s^<-1> for the excitation migration to the closest Ru(II). The mechanism of energy migration and transfer in the closest condition of metal centers are ascribed to electron exchange interaction.

对于倾斜的研究，飞秒腔倾倒钛：蓝宝石激光器已在日本首次建成。我们已经成功地将脉冲能量增加到10倍（35 fs，20 nJ/脉冲），具有可变重复频率（10 kHz-76 MHz），衍射效率（40-60%）。虽然我们在泵浦-探测测量双金属配合物晶体和光电导材料如氧钛酞菁薄膜中尝试过相位弛豫信号的测量，但目前还不能成功地从泵浦-探测测量中得到任何相位弛豫的信息。这是由于我们现有的泵浦探测系统信噪比不好以及纯晶体中存在的热问题造成的。我们试图将这种方法应用于稀固体体系，并利用这种激光系统组成的时间相关光子计数方法研究了掺杂晶体中的能量传递反应。在高掺杂的Os^<2+>：[Ru（bpy）_3]（PF_6）_2晶体中，^3CT（Ru）的基质发射衰减为非指数衰减。衰减归因于能量转移的各种速率常数取决于激发的主客体距离，这是改变作为通过主机分子的激发迁移的结果。通过随机模拟，确定最接近的Os（II）的速率为1.2 x <10>10^8 s^<-1>，<-1>激发迁移到最接近的Ru（II）的速率为3 x 10^8 s^。在金属中心最近距离条件下的能量迁移和传递机制属于电子交换作用。

项目成果

A.Islam et al.: "A Displaced and Low-frequency Vibration of Phosphorescent State of trans-[Rh(ethylenediamine)_2Cl_2]PF_6 in a Range of 5-497 K." J. Chem. Phys.109・12. 4900-4910 (1998)

A. Islam 等人：“反式[Rh(乙二胺)_2Cl_2]PF_6 在 5-497 K 范围内的位移和低频振动。J. Chem. 4900”。 -4910 (1998)

A.Islam et al.: "Dual ^3(d-d) Emission of [RhL_2Cl_2](PF_6) (L=2,2'-bipyridine and 1,10-phenanthroline) in a crystal in the temperature range of 77-536 K." J.Photochem.Photobiol.A : Chem.106(1-3). 61-66 (1997)

A.Islam 等人：“在 77-536 K 温度范围内晶体中 [RhL_2Cl_2](PF_6)（L=2,2-联吡啶和 1,10-菲咯啉）的双重 ^3(d-d) 发射

A.Islam et al.: "Dual^3 (d-d) Emission of [RhL_2Cl_2] (PF_6) (L=2,2'-bipyridine and 1,10-phenanthroline) in a crystal in the temperature range of 77-536 K." J.Photochem.Photobiol.A : Chem. 106・1-3. 61-66 (1997)

A.Islam 等人：“在 77-536 K 温度范围内，晶体中 [RhL_2Cl_2] (PF_6)（L=2,2-联吡啶和 1,10-菲咯啉）的 Dual^3 (d-d) 发射” J.Photochem.Photobiol.A：Chem. 106・1-3. 61-66 (1997)

A.Islam et al.: "A Displaced and Low-frequency Vibration of Phosphorescent State of trans-[Rh(ethylenediamine)_2Cl_2]PF_6 in a Range of 5-497 K." J.Chem.Phys.109(12). 4900-4910 (1998)

A.Islam 等人：“反式-[Rh(乙二胺)_2Cl_2]PF_6 在 5-497 K 范围内磷光态的位移和低频振动。”

A.Islam et al.: "Non-radiative Processes of Excited CT States of Ru(II) Compounds in the Solid State and at Higher Temperatures." Coord. Chem. Rev. 171. 353-363 (1998)

A.Islam 等人：“Ru(II) 化合物在固态和较高温度下的激发 CT 态的非辐射过程”。