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

Chábera, Pavel LU ; Kjaer, Kasper S. LU ; Prakash, Om LU ; Honarfar, Alireza LU ; Liu, Yizhu LU ; Fredin, Lisa A. LU ; Harlang, Tobias C.B. LU ; Lidin, Sven LU ; Uhlig, Jens LU and Sundström, Villy LU , et al. (2018) In Journal of Physical Chemistry Letters 9(3). p.459-463
Abstract

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... (More)

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. 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.

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Journal of Physical Chemistry Letters
volume
9
issue
3
pages
5 pages
publisher
The American Chemical Society
external identifiers
  • scopus:85041439699
ISSN
1948-7185
DOI
10.1021/acs.jpclett.7b02962
language
English
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yes
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f12e764a-a791-4524-a4cd-16f413eeedbf
date added to LUP
2018-02-21 10:47:21
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2018-09-23 04:55:38
@article{f12e764a-a791-4524-a4cd-16f413eeedbf,
  abstract     = {<p>The iron carbene complex [Fe<sup>II</sup>(btz)<sub>3</sub>](PF<sub>6</sub>)<sub>2</sub> (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 <sup>3</sup>MLCT state with a 528 ps excited-state lifetime in CH<sub>3</sub>CN solution that is more than one order of magnitude longer compared with the MLCT lifetime of any previously reported Fe<sup>II</sup> complex. The low potential of the [Fe(btz)<sub>3</sub>]<sup>3+</sup>/[Fe(btz)<sub>3</sub>]<sup>2+</sup> redox couple makes the <sup>3</sup>MLCT state of [Fe<sup>II</sup>(btz)<sub>3</sub>]<sup>2+</sup> a potent photoreductant that can be generated by light absorption throughout the visible spectrum. Taken together with our recent results on the [Fe<sup>III</sup>(btz)<sub>3</sub>]<sup>3+</sup> form of this complex, these results show that the Fe<sup>II</sup> and Fe<sup>III</sup> oxidation states of the same Fe(btz)<sub>3</sub> 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.</p>},
  author       = {Chábera, Pavel and Kjaer, Kasper S. and Prakash, Om and Honarfar, Alireza and Liu, Yizhu and Fredin, Lisa A. and Harlang, Tobias C.B. and Lidin, Sven and Uhlig, Jens and Sundström, Villy and Lomoth, Reiner and Persson, Petter and Wärnmark, Kenneth},
  issn         = {1948-7185},
  language     = {eng},
  month        = {02},
  number       = {3},
  pages        = {459--463},
  publisher    = {The American Chemical Society},
  series       = {Journal of Physical Chemistry Letters},
  title        = {Fe<sup>II</sup> Hexa N-Heterocyclic Carbene Complex with a 528 ps Metal-To-Ligand Charge-Transfer Excited-State Lifetime},
  url          = {http://dx.doi.org/10.1021/acs.jpclett.7b02962},
  volume       = {9},
  year         = {2018},
}