Ultrafast Excited-State Dynamics of Re(CO)3Cl(dcbpy) in Solution and on Nanocrystalline TiO2 and ZrO2 Thin Films
Ultrafast Excited-State Dynamics of Re(CO)3Cl(dcbpy) in Solution and on Nanocrystalline TiO2 and ZrO2 Thin Films
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Re(CO)3Cl(dcbpy) 在溶液中以及纳米晶 TiO2 和 ZrO2 薄膜上的超快激发态动力学
DOI：
10.1021/jp9936648
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发表时间：
2000
影响因子：
2.9
通讯作者：
T. Lian
中科院分区：
文献类型：
--
作者：
Yongqiang Wang;and John B. Asbury;T. Lian
飞秒红外光谱用于研究DMF溶液中RE（CO）3Cl（DCBPY）的激发态动力学以及在ZRO2和TIO2纳米晶体薄膜的表面上。对于DMF溶液中的RE（CO）3Cl（DCBPY），我们观察到了寿命长的3MLCT状态，其寿命> 1 ns。与基态的频率相比，CO拉伸带的频率是蓝班的，这与激发态的金属到配体的电荷转移性质一致。在前12 ps中观察到了激发态CO拉伸带的快速光谱演化。对于ZRO2薄膜上的RE（CO）3Cl（DCBPY），观察到类似的3MLCT态。但是，光谱蓝移的明显不足，并且在更快的时间尺度上发生。我们建议振动弛豫是对ZRO2膜上RE（CO）3Cl（DCBPY）光谱演化的主要贡献，而MLCT态的振动弛豫和溶剂化均有助于DMF溶液中的光谱演化。激发态衰减率o ...
Femtosecond infrared spectroscopy was used to study the excited-state dynamics of Re(CO)3Cl(dcbpy) in DMF solution and on the surface of ZrO2 and TiO2 nanocrystalline thin films. For Re(CO)3Cl(dcbpy) in DMF solution, we observed a long-lived 3MLCT state with a lifetime of >1 ns. The frequencies for the CO stretching bands were blue-shifted compared to those in the ground state, consistent with the metal-to-ligand charge-transfer nature of the excited state. Rapid spectral evolution of the excited-state CO stretching bands was observed within the first 12 ps. For Re(CO)3Cl(dcbpy) on ZrO2 thin films, a similar 3MLCT state was observed. However, the spectral blue shift was much less pronounced and occurred on a faster time scale. We suggest that vibrational relaxation is the primary contribution to the spectral evolution of Re(CO)3Cl(dcbpy) on the ZrO2 film, whereas both vibrational relaxation and solvation of the MLCT state contribute to the spectral evolution in DMF solution. The excited-state decay rate o...