FeII Hexa N-Heterocyclic Carbene Complex with a 528 ps Metal-to-Ligand Charge-Transfer Excited-State Lifetime

Chábera, Pavel; Kjaer, Kasper S.; Prakash, Om; Honarfar, Alireza; Liu, Yizhu; Fredin, Lisa A.; Harlang, Tobias C.  B.; Lidin, Sven; Uhlig, Jens; Sundström, Villy; Lomoth, Reiner; Persson, Petter; Wärnmark, Kenneth

doi:10.1021/acs.jpclett.7b02962

Title: Fe^II Hexa N-Heterocyclic Carbene Complex with a 528 ps Metal-to-Ligand Charge-Transfer Excited-State Lifetime

Journal Article · Wed Jan 03 00:00:00 EST 2018 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.7b02962· OSTI ID:1471519

^[1]; Kjaer, Kasper S. ^[2];

^[3]; Honarfar, Alireza ^[1];

^[3];

^[4]; Harlang, Tobias C. B. ^[1];

^[3]; Uhlig, Jens ^[1];

^[1]; Lomoth, Reiner ^[5];

^[4];

^[3]

Lund Univ. (Sweden). Division of Chemical Physics
Lund Univ. (Sweden). Division of Chemical Physics; SLAC National Accelerator Lab., Menlo Park, CA (United States). PULSE Inst.
Lund Univ. (Sweden). Center for Analysis and Synthesis (CAS)
Lund Univ. (Sweden). Division of Theoretical Chemistry
Uppsala Univ. (Sweden). Dept. of Chemistry. Ångström Lab.

In this paper, the iron carbene complex [Fe^II(btz)₃](PF₆)₂ (where btz = 3,3'-dimethyl-1,1'-bis(p-tolyl)-4,4'-bis(1,2,3-triazol-5-ylidene)) has been synthesized, isolated, and characterized as a low-spin ferrous complex. It exhibits strong metal-to-ligand charge transfer (MLCT) absorption bands throughout the visible spectrum, and excitation of these bands gives rise to a ³MLCT state with a 528 ps excited-state lifetime in CH₃CN solution that is more than one order of magnitude longer compared with the MLCT lifetime of any previously reported Fe^II complex. The low potential of the [Fe(btz)₃]³⁺/[Fe(btz)₃]²⁺ redox couple makes the ³MLCT state of [Fe^II(btz)₃]²⁺ a potent photoreductant that can be generated by light absorption throughout the visible spectrum. Finally, taken together with our recent results on the [Fe^III(btz)₃]³⁺ form of this complex, these results show that the Fe^II and Fe^III oxidation states of the same Fe(btz)₃ complex feature long-lived MLCT and LMCT states, respectively, demonstrating the versatility of iron N-heterocyclic carbene complexes as promising light-harvesters for a broad range of oxidizing and reducing conditions.

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Research Organization:: SLAC National Accelerator Lab., Menlo Park, CA (United States); Lund Univ. (Sweden); Uppsala Univ. (Sweden)

Sponsoring Organization:: USDOE; Knut and Alice Wallenberg Foundation (Sweden); Swedish Energy Agency (Energimyndigheten); Swedish Research Council (VR); Crafoord Foundation (Sweden); Danish Council for Independent Research (Denmark)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1471519

Journal Information:: Journal of Physical Chemistry Letters, Vol. 9, Issue 3; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 112 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: FeII Hexa N-Heterocyclic Carbene Complex with a 528 ps Metal-to-Ligand Charge-Transfer Excited-State Lifetime

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