Relaxation dynamics of [Re(CO)2(bpy){P(OEt)3}2](PF6) in TEOA solvent measured by time-resolved attenuated total reflection terahertz spectroscopy
Relaxation dynamics of [Re(CO)2(bpy){P(OEt)3}2](PF6) in TEOA solvent measured by time-resolved attenuated total reflection terahertz spectroscopy
复制标题
通过时间分辨衰减全反射太赫兹光谱测量 TEOA 溶剂中 [Re(CO)2(bpy){P(OEt)3}2](PF6) 的弛豫动力学
DOI：
10.1038/s41598-019-48191-4
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发表时间：
2019
影响因子：
4.6
通讯作者：
Kimura Shin-ichi
中科院分区：
文献类型：
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作者：
Nguyen Phuong Ngoc;Watanabe Hiroshi;Tamaki Yusuke;Ishitani Osamu;Kimura Shin-ichi
为了揭示人工光合作用材料[Re（CO）2（bpy）{P（OEt）3}2]（PF 6）的高效光催化性能，采用时间分辨衰减全反射光谱技术，在太赫兹波段直接观测了以三乙醇胺（TEOA）为电子供体的光合作用材料的光诱导弛豫动力学和光激发态的还原猝灭过程. TEOA中络合物的光谱在络合物和TEOA分子之间具有分子间振动模式，这反映了还原猝灭过程的前兆。光激发后，分子间振动模式在皮秒时间尺度内经历了三步弛豫过程：首先，三重态金属-配体电荷转移激发态被振动冷却;其次，热传递加速了TEOA分子间的偶极-偶极相互作用，导致TEOA分子旋转，从而缩短了Re与TEOA分子间的距离;这些结果为[Re（CO）2（bpy）{P（OEt）3}2]（PF 6）在TEOA溶剂中光催化性能的电子转移过程提供了详细的信息。
To reveal highly efficient photocatalytic properties of an artificial photosynthesis material [Re(CO)2(bpy){P(OEt)3}2](PF6), we have directly observed the photo-induced relaxation dynamics and reductive quenching process of the photo-excited state on a photosynthesis material in Triethanolamine (TEOA) solvent as an electron donor by time-resolved attenuated total reflection spectroscopy in the terahertz (THz) region. The spectrum of the complex in TEOA has an intermolecular vibrational mode between the complex and TEOA molecules, which reflects the precursor of the reductive quenching process. The intermolecular vibrational mode has three-step relaxation process in a picosecond timescale after photo-excitation, where firstly the triplet metal-to-ligand charge transfer excited state is vibrationally cooled down, secondly the distance between Re and TEOA is reduced by the rotation of TEOA molecules due to dipole-dipole interaction accelerated by heat transfer, and finally electrons transfer from TEOA to Re. These observations provide us the detailed information of the electron transfer process of photocatalytic properties of [Re(CO)2(bpy){P(OEt)3}2](PF6) in TEOA solvent.