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

Journal Article · · Journal of Physical Chemistry Letters
 [1];  [2];  [3];  [1];  [3];  [4];  [1];  [3];  [1];  [1];  [5];  [4];  [3]
  1. Lund Univ. (Sweden). Division of Chemical Physics
  2. Lund Univ. (Sweden). Division of Chemical Physics; SLAC National Accelerator Lab., Menlo Park, CA (United States). PULSE Inst.
  3. Lund Univ. (Sweden). Center for Analysis and Synthesis (CAS)
  4. Lund Univ. (Sweden). Division of Theoretical Chemistry
  5. Uppsala Univ. (Sweden). Dept. of Chemistry. Ångström Lab.
+ Show Author Affiliations

In this paper, the iron carbene complex [FeII(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 FeII complex. The low potential of the [Fe(btz)3]3+/[Fe(btz)3]2+ redox couple makes the 3MLCT state of [FeII(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 [FeIII(btz)3]3+ form of this complex, these results show that the FeII and FeIII 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.

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, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 3 Vol. 9; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy journal October 2019
Blue-Emissive Cobalt(III) Complexes and Their Use in the Photocatalytic Trifluoromethylation of Polycyclic Aromatic Hydrocarbons journal June 2018
Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy journal January 2020
Is Iron the New Ruthenium? journal February 2019
Excited‐State Kinetics of an Air‐Stable Cyclometalated Iron(II) Complex journal June 2019
Toward Luminescent Iron Complexes: Unravelling the Photophysics by Computing Potential Energy Surfaces journal May 2019
Towards Noble-Metal-Free Dyads: Ground and Excited State Tuning by a Cobalt Dimethylglyoxime Motif Connected to an Iron N-Heterocyclic Carbene Photosensitizer: Towards Noble-Metal-Free Dyads: Ground and Excited State Tuning by a Cobalt Dimethylglyoxime Motif Connected to an Iron N-Heterocyclic Carbene Photose journal December 2018
Photophysical properties of bichromophoric Fe(II) complexes bearing an aromatic electron acceptor journal June 2019
Iron(ii) coordination complexes with panchromatic absorption and nanosecond charge-transfer excited state lifetimes journal November 2019
Photoredox catalysts based on earth-abundant metal complexes journal January 2019
Photoexcited state chemistry of metal–oxygen complexes journal January 2018
Designing air-stable cyclometalated Fe( ii ) complexes: stabilization via electrostatic effects journal January 2019
Band-selective dynamics in charge-transfer excited iron carbene complexes journal January 2019
Insights into the excited state dynamics of Fe( ii ) polypyridyl complexes from variable-temperature ultrafast spectroscopy journal January 2019
Photophysics and photochemistry with Earth-abundant metals – fundamentals and concepts journal January 2020
Iron( ii ) complexes with diazinyl-NHC ligands: impact of π-deficiency of the azine core on photophysical properties journal January 2019
Revealing the initial steps in homogeneous photocatalysis by time-resolved spectroscopy journal January 2020
Luminescence and reactivity of a charge-transfer excited iron complex with nanosecond lifetime journal November 2018
Electronic structure in the transition metal block and its implications for light harvesting journal January 2019
Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy text January 2020
Design and Synthesis of Photoactive Iron N-Heterocyclic Carbene Complexes journal January 2020
Improving the Light-Induced Spin Transition Efficiency in Ni(II)-Based Macrocyclic-Ligand Complexes journal November 2019
Is Iron the New Ruthenium? text January 2019

Figures / Tables (4)

Figure 1.(p. 2)figure Figure 1.
Figure 2.(p. 2)figure Figure 2.
Figure 3.(p. 2)figure Figure 3.
Figure 4.(p. 3)figure Figure 4.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY