Probing Interligand Electron Transfer in the 1MLCT S1 Excited State of trans-Mo2L2L′2 Compounds: A Comparative Study of Auxiliary Ligands and Solvents
| Autor: | Samantha E. Brown-Xu, Ewan J. M. Hamilton, Judith C. Gallucci, Malcolm H. Chisholm, Changcheng Jiang, Philip J. Young, William T. Kender |
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| Rok vydání: | 2017 |
| Předmět: |
Electron density
010405 organic chemistry Ligand Infrared 010402 general chemistry Photochemistry 01 natural sciences 0104 chemical sciences Inorganic Chemistry Electron transfer chemistry.chemical_compound chemistry Excited state Carboxylate Singlet state Physical and Theoretical Chemistry Spectroscopy |
| Zdroj: | Inorganic Chemistry. 56:9660-9668 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/acs.inorgchem.7b01164 |
| Popis: | The interligand charge dynamics of the lowest singlet metal-to-ligand charge-transfer states (1MLCT S1 states) of a series of quadruply bonded trans-Mo2(NN)2(O2C–X)2 paddlewheel compounds are investigated, where NN is a π-accepting phenylpropiolamidinate ligand and O2C–X (X = Me, tBu, TiPB, or CF3) is an auxiliary carboxylate ligand. The compounds show strong light absorption in the visible region due to MLCT transitions from the Mo2 center to the NN ligands. The transferred electron density was followed by femtosecond time-resolved infrared (fs-TRIR) spectroscopy with vibrational reporters such as the ethynyl groups on the NN ligands. The observed fs-TRIR spectra show that these compounds have asymmetric 1MLCT S1 excited states where the transferred electron mainly resides on a single NN ligand. The presence of interligand electron transfer (ILET) is suggested to explain the shape of the ν(C≡C) bands and the influence of auxiliary ligands and solvents on the interligand electronic coupling. The ILET in t... |
| Databáze: | OpenAIRE |
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