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Journal Article

A heteroleptic ferrous complex with mesoionic bis(1,2,3-triazol-5-ylidene) ligands: Taming the MLCT excited state of iron(II).

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Canton,  S. E.
Research Group of Structural Dynamics of (Bio)Chemical Systems, MPI for Biophysical Chemistry, Max Planck Society;

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Citation

Liu, Y., Kjær, K. S., Fredin, L. A., Chábera, P., Harlang, T., Canton, S. E., et al. (2015). A heteroleptic ferrous complex with mesoionic bis(1,2,3-triazol-5-ylidene) ligands: Taming the MLCT excited state of iron(II). Chemistry - A European Journal, 21(9), 2628-2639. doi:10.1002/chem.201405184.


Cite as: https://hdl.handle.net/11858/00-001M-0000-002D-7C0D-C
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.