Ground State Nuclear Magnetic Resonance Chemical Shifts Predict Charge-Separated Excited State Lifetimes
| Autor: | Dominic K. Kersi, Casseday P. Richers, Changjian Feng, Logan J. Giles, Ranjana Dangi, David A. Shultz, Jing Yang, Christopher R. Tichnell, Benjamin W. Stein, Martin L. Kirk |
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| Rok vydání: | 2018 |
| Předmět: |
X-ray absorption spectroscopy
Chemistry Chemical shift 02 engineering and technology Carbon-13 NMR 010402 general chemistry 021001 nanoscience & nanotechnology Photochemistry 01 natural sciences Acceptor 0104 chemical sciences Inorganic Chemistry Chalcogen Excited state Physical and Theoretical Chemistry 0210 nano-technology Ground state Diimine |
| Zdroj: | Inorganic Chemistry. 57:13470-13476 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/acs.inorgchem.8b02087 |
| Popis: | Dichalcogenolene platinum(II) diimine complexes, (LE,E′)Pt(bpy), are characterized by charge-separated dichalcogenolene donor (LE,E′) → diimine acceptor (bpy) ligand-to-ligand charge transfer (LL′CT) excited states that lead to their interesting photophysics and potential use in solar energy conversion applications. Despite the intense interest in these complexes, the chalcogen dependence on the lifetime of the triplet LL′CT excited state remains unexplained. Three new (LE,E′)Pt(bpy) complexes with mixed chalcogen donors exhibit decay rates that are dominated by a spin–orbit mediated nonradiative pathway, the magnitude of which is proportional to the anisotropic covalency provided by the mixed-chalcogen donor ligand environment. This anisotropic covalency is dramatically revealed in the 13C NMR chemical shifts of the donor carbons that bear the chalcogens and is further probed by S K-edge XAS. Remarkably, the NMR chemical shift differences also correlate with the spin–orbit matrix element that connects th... |
| Databáze: | OpenAIRE |
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