Pinpointing the Extent of Electronic Delocalization in the Re(I)-to-Tetrazine Charge-Separated Excited State Using Time-Resolved Infrared Spectroscopy

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• 作者：Guifeng Li ; Kumar Parimal ; Shubham Vyas ; Christopher M. Hadad ; Amar H. Flood ; Ksenija D. Glusac
• 刊名：Journal of the American Chemical Society
• 出版年：2009
• 出版时间：August 26, 2009
• 年：2009
• 卷：131
• 期：33
• 页码：11656-11657
• 全文大小：141K
• 年卷期：v.131,no.33(August 26, 2009)
• ISSN：1520-5126

文摘

Femtosecond mid-IR transient absorption spectroscopy (TRIR) and time-dependent density functional theory (TD-DFT) calculations on Re(CO)₃Cl(Me₂BPTZ) [Me₂BPTZ = 3,6-bis(5-methyl-2-pyridine)-1,2,4,5-tetrazine] are used to demonstrate that the lowest excited state of the complex is a triplet metal-to-ligand charge-transfer (³MLCT) state with a lifetime of 225 ps. The short excited-state lifetime is explained by the energy-gap law. Vibrational cooling of the ³MLCT state shows up as early-time dynamics (3.6 ps). The structural changes in the excited state are deduced from the frequency shifts in the TRIR vibrational bands. The vibrational frequencies of the CO groups increase upon excitation as a result of decreased back-bonding between the CO ligands and the oxidized Re center in the ³MLCT state. The vibrational frequencies of the central tetrazine ring of Me₂BPTZ decrease because of the decrease in the bond order upon reduction of the Me₂BPTZ ligand in the ³MLCT state. Interestingly, the TRIR signals from the pyridine moieties of Me₂BPTZ were not detected. These results can be explained by localization of the electronic charge on the central tetrazine ring in the ³MLCT state of Re(CO)₃Cl(Me₂BPTZ), as supported by TD-DFT calculations.