A Heteroleptic Ferrous Complex with Mesoionic Bis(1,2,3-triazol-5-ylidene) Ligands: Taming the MLCT Excited State of Iron(II).

Yizhu Liu, Kasper Kjaer, Lisa Fredin, Pavel Chabera, Tobias Harlang, Sophie Canton, Sven Lidin, Jianxin Zhang, Reiner Lomoth, Karl-Erik Bergquist, Petter Persson, Kenneth Wärnmark, Villy Sundström

Forskningsoutput: TidskriftsbidragArtikel i vetenskaplig tidskriftPeer review

Sammanfattning

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, The efficient synthesis of a heteroleptic Fe(II) complex (1) is based on sequentially furnishing the Fe(II) 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 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 ((3) MLCT) state in 1, rendering it a lifetime of 13 ps, the longest to date of a photochemically stable Fe(II) complex. Deactivation of the (3) MLCT state is proposed to proceed via the (3) MC state that strongly couples with the singlet ground state.
Originalspråkengelska
Sidor (från-till)3628-3639
TidskriftChemistry: A European Journal
Volym21
Nummer9
DOI
StatusPublished - 2015

Bibliografisk information

The information about affiliations in this record was updated in December 2015.
The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039), Centre for Analysis and Synthesis (011001266), Chemical Physics (S) (011001060), Department of Chemistry (011001220)

Ämnesklassifikation (UKÄ)

  • Teoretisk kemi
  • Kemi
  • Atom- och molekylfysik och optik

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