Femtosecond Dynamics 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

• 批准号: 11640510
• 负责人: IKEDA Noriaki
• 金额: $ 2.3万
• 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: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640510/
• 关键词: Metal Complex; Thin-crystalline Film; Femtosecond Laser-photolysis; Oxotitanium-phthalocyanines; Ruthenium Complexes; Monte Carlo simulation; Electron Transfer; Energy Transfer; ホール; 結晶

1. Photoprimary processes of various thin crystals of oxotitanium (IV) phthalocyanine (OTiPc)_n revealed by femtosecond laser photolysis. A rapid change of the transient absorption spectrum showed that a part of the exciton of β-OTiPc was in 1 ps converted to an one-electron oxidized species, (OTiPc)_n^+, then the hole disappeared in 20 ps. Most of the ground-state was recovered within 50 ps. The conversion to (OTiPc)_n^+ was less clear for α-OTiPc. Quantum yields and lifetimes of fluorescence for the crystals of OTiPc were also determined. A fluorescence with a peak at 10,420cm^<-1> from α-OTiPc exhibited biexponential decay of a major relaxed exciton with 35-65 ps and a minor relaxed exciton with 100-424 ps. An increase in the initial intensity of the short-lived fluorescence at 77 K indicates that the relaxed exciton is a minor product of the excitation of α-OTiPc at 298 K.A charge-carrier formation by photo-excitation seems to be much faster than the internal conversion to the rela … More xed exciton.2. Determination of distance-dependent rate-constants of excitation energy transfer and hopping in the crystalline solids of [Os_xRu_<1-x>(bpy)_3]X_2 with various counter ions. Non-linear decays of the emission in the crystals of [Ru(bpy)_3]X_2 doped with Os(II) have been analyzed and simulated by a Monte Carlo method. Molecular interaction via electron exchange type is predominant for the energy transfer of ^3MLCT(Ru) to Os^<2+> in the close proximity and for the hopping of ^3MLCT(Ru) to the nearest neighbor. The rate constants for the energy transfer to Os^<2+> and hopping were determined at various distances. A distance attenuation factor (12.5 nm^<-1>) obtained for the electronic exchange interaction was small compared with reference values.Time-resolved absorption spectroscopy for the neat crystal revealed that T-T annihilation produced the one-electron transferred products. Rate of electron transfer between ^3MLCT in the neat crystal of [Ru(bpy)_3](PF_6)_2 was estimated to be more than 5x10^<10>s^<-1>. Less

1.飞秒激光光解揭示酞菁氧钛（IV）（OTiPc）_n各种薄晶体的光初级过程。瞬态吸收谱的快速变化表明，在1 ps内，β-OTiPc的部分激子转变为单电子氧化态（OTiPc）_n^+，空穴在20 ps内消失。在50 ps内，大部分基态被恢复。α-OTiPc向（OTiPc）_n^+的转化不太清楚。还测定了OTiPc晶体的量子产率和荧光寿命。α-OTiPc在10，420 cm-2处的荧光峰<-1>显示出双指数衰减，主要弛豫激子的衰减为35-65 ps，次要弛豫激子的衰减为100-424 ps。在77 K时短寿命荧光的初始强度增加表明弛豫激子是α-OTiPc在298 K时激发的次要产物。光激发形成载流子的速度似乎比内转换到相对论的速度快得多。 ...更多信息 固定激子2. [Os_xRu_（bpy）_3]X_2晶体中与不同反离子的激发能转移和跳跃速率常数的测定<1-x>本文用Monte Carlo方法分析和模拟了掺Os（II）的[Ru（bpy）_3]X_2晶体中发射的非线性衰减。通过电子交换型的分子相互作用对于^3MLCT（Ru）到邻近的Os^&lt;2+&gt;的能量转移和^3MLCT（Ru）到最近邻的跳跃是主要的。在不同的距离下测定了向Os^&lt;2+&gt;的能量转移和跳跃的速率常数。电子交换作用的距离衰减因子（12.5 nm<-1>）与参考值相比很小，时间分辨吸收光谱表明T-T湮没产生了单电子转移产物。在[Ru（bpy）_3]（PF_6）_2纯晶体中，^3MLCT之间的电子转移速率大于5 × 10 ~（-6）<10>s ~（-1）<-1>。少

项目成果

N.Ikeda et al.: "Hopping and Annihilation of ^3MLCT in the Crystalline Solid of [Ru(bpy)_3]X_2(X=Cl^-,ClO_4^-and PF_6)."J.Phys.Chem.A. 104・26. 6158-6164 (2000)

N. Ikeda 等人：“[Ru(bpy)_3]X_2(X=Cl^-,ClO_4^-and PF_6) 晶体固体中 ^3MLCT 的跳跃和湮灭。”J.Phys.Chem.A. 104・26。6158-6164（2000）

M.Tsushima et al.: "Solid-State-Photochemistry : Energy-Transfer and Electron-Transfer of ^3CT in Crystals of [Os_xRu_<1-x>(bpy)_3]X_2(x=0-0.23)."Coord.Chem.Rev.. 208・. 299-308 (2000)

M.Tsushima 等人：“固态光化学：[Os_xRu_<1-x>(bpy)_3]X_2(x=0-0.23) 晶体中 ^3CT 的能量转移和电子转移。”坐标.化学评论.208・.299-308(2000)

M.Tsushima, N.Ikeda, A.Yoshimura, K.Nozaki, and T.Ohno: "Solid-State-Photochemistry : Energy-Transfer and Electron-Transfer of ^3CT in Crystals of [Os_xRu_<1-x>(bpy)_3]X_2(x=0-0.23)."Coord.Chem.Rev.. 208. 299-308 (2000)

M.Tsushima、N.Ikeda、A.Yoshimura、K.Nozaki 和 T.Ohno：“固态光化学：[Os_xRu_<1-x>(bpy) 晶体中 ^3CT 的能量转移和电子转移”

Ikeda et al.: "Hopping and Annihilation of ^3MLCT in the Crystalline Solid of [Ru(bpy)_3]X_2 (X=Cl^-,ClO^-_4 and PF_6)"J. Phys. Chem. A.. (in-press). (2000)

Ikeda 等人：“[Ru(bpy)_3]X_2 (X=Cl^-,ClO^-_4 和 PF_6) 晶体固体中 ^3MLCT 的跳跃和湮灭”J.

M.Tsushima, N.Ikeda, K.Nozaki, and T.Ohno: "Fast Energy Transfer of ^3CT of [Ru(bpy)_3](PF_6)_2 to Os^<2+> at Short Distances in the Crystal."J.Phys.Chem.A. 104. 5176-5180 (2000)

M.Tsushima、N.Ikeda、K.Nozaki 和 T.Ohno：“[Ru(bpy)_3](PF_6)_2 的 ^3CT 在晶体中短距离快速能量转移到 Os^<2>”。