期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 21, 期 9, 页码 3628-3639出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201405184
关键词
iron; femtosecond spectroscopy; N ligands; metal-to-ligand charge transfer; N-heterocyclic carbenes
资金
- Crafoord Foundation
- Swedish Research Council (VR)
- Knut and Alice Wallenberg (KAW) Foundation
- European Research Council (ERC) [226136-VISCHEM]
- Swedish Energy Agency
Strongly sigma-donating N-heterocyclic carbenes (NHCs) have revived research interest in the catalytic chemistry of iron, and are now also starting to bring the photochemistry and photophysics of this abundant element into a new era. In this work, a heteroleptic Fe-II complex (1) was synthesized based on sequentially furnishing the Fe-II center with the benchmark 2,2-bipyridine (bpy) ligand and the more strongly sigma-donating mesoionic ligand, 4,4-bis(1,2,3-triazol-5-ylidene) (btz). Complex1 was comprehensively characterized by electrochemistry, static and ultrafast spectroscopy, and quantum chemical calculations and compared to [Fe(bpy)(3)](PF6)(2) and (TBA)(2)[Fe(bpy)(CN)(4)]. Heteroleptic complex1 extends the absorption spectrum towards longer wavelengths compared to a previously synthesized homoleptic Fe-II NHC complex. The combination of the mesoionic nature of btz and the heteroleptic structure effectively destabilizes the metal-centered (MC) states relative to the triplet metal-to-ligand charge transfer ((MLCT)-M-3) state in 1, rendering it a lifetime of 13ps, the longest to date of a photochemically stable Fe-II complex. Deactivation of the (MLCT)-M-3 state is proposed to proceed via the (MC)-M-3 state that strongly couples with the singlet ground state.
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