Exceptional Excited-State Lifetime of an Iron(II)-N-Heterocyclic Carbene Complex Explained
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/4609128
- author
- Fredin, Lisa LU ; Papai, Matyas ; Rozsalyi, Emese ; Vanko, Gyoergy ; Wärnmark, Kenneth LU ; Sundström, Villy LU and Persson, Petter
- organization
- publishing date
- 2014
- 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}}, }