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- Title
A Heteroleptic Ferrous Complex with Mesoionic Bis(1,2,3-triazol-5-ylidene) Ligands: Taming the MLCT Excited State of Iron(II).
- Authors
Liu, Yizhu; Kjær, Kasper S.; Fredin, Lisa A.; Chábera, Pavel; Harlang, Tobias; Canton, Sophie E.; Lidin, Sven; Zhang, Jianxin; Lomoth, Reiner; Bergquist, Karl ‐ Erik; Persson, Petter; Wärnmark, Kenneth; Sundström, Villy
- Abstract
Strongly σ-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 FeII complex ( 1) was synthesized based on sequentially furnishing the FeII center with the benchmark 2,2′-bipyridine (bpy) ligand and the more strongly σ-donating mesoionic ligand, 4,4′-bis(1,2,3-triazol-5-ylidene) (btz). Complex 1 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 complex 1 extends the absorption spectrum towards longer wavelengths compared to a previously synthesized homoleptic FeII 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 (3MLCT) state in 1, rendering it a lifetime of 13 ps, the longest to date of a photochemically stable FeII complex. Deactivation of the 3MLCT state is proposed to proceed via the 3MC state that strongly couples with the singlet ground state.
- Subjects
MESOIONIC compounds; HETEROCYCLIC compounds; LIGAND exchange reactions; CARBENES; IRON; PHOTOCHEMISTRY; CHARGE transfer
- Publication
Chemistry - A European Journal, 2015, Vol 21, Issue 9, p3628
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201405184