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Exceptional Excited-State Lifetime of an Iron(II)-N-Heterocyclic Carbene Complex Explained

Fredin, Lisa LU ; Papai, Matyas ; Rozsalyi, Emese ; Vanko, Gyoergy ; Wärnmark, Kenneth LU ; Sundström, Villy LU and Persson, Petter (2014) In The Journal of Physical Chemistry Letters 5(12). p.2066-2071
Abstract
Earth-abundant transition-metal complexes are desirable for sensitizers in dye-sensitized solar cells or photocatalysts. Iron is an obvious choice, but the energy level structure of its typical polypyridyl complexes, featuring low-lying metal-centered states, has made such complexes useless as energy converters. Recently, we synthesized a novel iron-N-heterocyclic carbene complex exhibiting a remarkable 100-fold increase of the lifetime compared to previously known iron(II) complexes. Here, we rationalize the measured excited-state dynamics with DFT and TD-DFT calculations. The calculations show that the exceptionally long excited-state lifetime (similar to 9 ps) is achieved for this Fe complex through a significant destabilization of both... (More)
Earth-abundant transition-metal complexes are desirable for sensitizers in dye-sensitized solar cells or photocatalysts. Iron is an obvious choice, but the energy level structure of its typical polypyridyl complexes, featuring low-lying metal-centered states, has made such complexes useless as energy converters. Recently, we synthesized a novel iron-N-heterocyclic carbene complex exhibiting a remarkable 100-fold increase of the lifetime compared to previously known iron(II) complexes. Here, we rationalize the measured excited-state dynamics with DFT and TD-DFT calculations. The calculations show that the exceptionally long excited-state lifetime (similar to 9 ps) is achieved for this Fe complex through a significant destabilization of both triplet and quintet metal-centered scavenger states compared to other Feu complexes. In addition, a shallow (MLCT)-M-3 potential energy surface with a low-energy transition path from the (MLCT)-M-3 to (MC)-M-3 and facile crossing from the (MC)-M-3 state to the ground state are identified as key features for the excited-state deactivation. (Less)
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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Letters
volume
5
issue
12
pages
2066 - 2071
publisher
The American Chemical Society (ACS)
external identifiers
  • wos:000337870100003
  • scopus:84903216322
  • pmid:26270494
ISSN
1948-7185
DOI
10.1021/jz500829w
language
English
LU publication?
yes
additional info
The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Centre for Analysis and Synthesis (011001266), Chemical Physics (S) (011001060), Department of Chemistry (011001220)
id
6091db5e-c4ff-4757-b452-e28dbe1b5d8e (old id 4609128)
date added to LUP
2016-04-01 13:48:44
date last changed
2022-03-29 17:27:47
@article{6091db5e-c4ff-4757-b452-e28dbe1b5d8e,
  abstract     = {{Earth-abundant transition-metal complexes are desirable for sensitizers in dye-sensitized solar cells or photocatalysts. Iron is an obvious choice, but the energy level structure of its typical polypyridyl complexes, featuring low-lying metal-centered states, has made such complexes useless as energy converters. Recently, we synthesized a novel iron-N-heterocyclic carbene complex exhibiting a remarkable 100-fold increase of the lifetime compared to previously known iron(II) complexes. Here, we rationalize the measured excited-state dynamics with DFT and TD-DFT calculations. The calculations show that the exceptionally long excited-state lifetime (similar to 9 ps) is achieved for this Fe complex through a significant destabilization of both triplet and quintet metal-centered scavenger states compared to other Feu complexes. In addition, a shallow (MLCT)-M-3 potential energy surface with a low-energy transition path from the (MLCT)-M-3 to (MC)-M-3 and facile crossing from the (MC)-M-3 state to the ground state are identified as key features for the excited-state deactivation.}},
  author       = {{Fredin, Lisa and Papai, Matyas and Rozsalyi, Emese and Vanko, Gyoergy and Wärnmark, Kenneth and Sundström, Villy and Persson, Petter}},
  issn         = {{1948-7185}},
  language     = {{eng}},
  number       = {{12}},
  pages        = {{2066--2071}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{The Journal of Physical Chemistry Letters}},
  title        = {{Exceptional Excited-State Lifetime of an Iron(II)-N-Heterocyclic Carbene Complex Explained}},
  url          = {{http://dx.doi.org/10.1021/jz500829w}},
  doi          = {{10.1021/jz500829w}},
  volume       = {{5}},
  year         = {{2014}},
}