Influence of Triplet Surface Properties on Excited-State Deactivation of Expanded Cage Bis(tridentate)Ruthenium(II) Complexes
(2019) In Journal of Physical Chemistry A 123(25). p.5293-5299- Abstract
Calculations of excited-state potential energy surfaces (PESs) are useful to predict key properties relating to the deactivation cascade of transition-metal complexes. Here, we first perform full free optimizations of the relevant excited-state minima, followed by extensive two-dimensional PES calculations based on the minima of interest. Maps of the lowest triplet excited-state surfaces of two bistridentate RuII-complexes, [Ru(DQP)2]2+ and [Ru(DQzP)2]2+, are used to explain recent experimental findings including an unexpected order of magnitude difference in an excited-state lifetime. The calculations reveal significant differences in the fundamental shapes and spin transitions of... (More)
Calculations of excited-state potential energy surfaces (PESs) are useful to predict key properties relating to the deactivation cascade of transition-metal complexes. Here, we first perform full free optimizations of the relevant excited-state minima, followed by extensive two-dimensional PES calculations based on the minima of interest. Maps of the lowest triplet excited-state surfaces of two bistridentate RuII-complexes, [Ru(DQP)2]2+ and [Ru(DQzP)2]2+, are used to explain recent experimental findings including an unexpected order of magnitude difference in an excited-state lifetime. The calculations reveal significant differences in the fundamental shapes and spin transitions of the lowest triplet excited-state energy surfaces of the two complexes and, in particular, show that the metal-to-ligand charge transfer (MLCT) surface region of [Ru(DQzP)2]2+ with a shorter excited-state lifetime is significantly smaller than that of [Ru(DQP)2]2+. This leads to a minimum energy crossing between the triplet and singlet surfaces near the MLCT for [Ru(DQzP)2]2+ or near the MC for [Ru(DQP)2]2+. These results indicate that the experimentally observed difference in the excited-state lifetime is closely related to the set of energetically accessible 3MLCT conformations.
(Less)
- author
- Fredin, Lisa A. LU and Persson, Petter LU
- organization
- publishing date
- 2019-06-05
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Journal of Physical Chemistry A
- volume
- 123
- issue
- 25
- pages
- 7 pages
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- scopus:85067955288
- pmid:31199149
- ISSN
- 1089-5639
- DOI
- 10.1021/acs.jpca.9b02927
- language
- English
- LU publication?
- yes
- id
- dd544e00-6430-4751-9ef5-e1838ebf1d59
- date added to LUP
- 2019-07-10 15:52:26
- date last changed
- 2024-04-02 12:46:11
@article{dd544e00-6430-4751-9ef5-e1838ebf1d59,
abstract = {{<p>Calculations of excited-state potential energy surfaces (PESs) are useful to predict key properties relating to the deactivation cascade of transition-metal complexes. Here, we first perform full free optimizations of the relevant excited-state minima, followed by extensive two-dimensional PES calculations based on the minima of interest. Maps of the lowest triplet excited-state surfaces of two bistridentate Ru<sup>II</sup>-complexes, [Ru(DQP)<sub>2</sub>]<sup>2+</sup> and [Ru(DQzP)<sub>2</sub>]<sup>2+</sup>, are used to explain recent experimental findings including an unexpected order of magnitude difference in an excited-state lifetime. The calculations reveal significant differences in the fundamental shapes and spin transitions of the lowest triplet excited-state energy surfaces of the two complexes and, in particular, show that the metal-to-ligand charge transfer (MLCT) surface region of [Ru(DQzP)<sub>2</sub>]<sup>2+</sup> with a shorter excited-state lifetime is significantly smaller than that of [Ru(DQP)<sub>2</sub>]<sup>2+</sup>. This leads to a minimum energy crossing between the triplet and singlet surfaces near the MLCT for [Ru(DQzP)<sub>2</sub>]<sup>2+</sup> or near the MC for [Ru(DQP)<sub>2</sub>]<sup>2+</sup>. These results indicate that the experimentally observed difference in the excited-state lifetime is closely related to the set of energetically accessible <sup>3</sup>MLCT conformations.</p>}},
author = {{Fredin, Lisa A. and Persson, Petter}},
issn = {{1089-5639}},
language = {{eng}},
month = {{06}},
number = {{25}},
pages = {{5293--5299}},
publisher = {{The American Chemical Society (ACS)}},
series = {{Journal of Physical Chemistry A}},
title = {{Influence of Triplet Surface Properties on Excited-State Deactivation of Expanded Cage Bis(tridentate)Ruthenium(II) Complexes}},
url = {{http://dx.doi.org/10.1021/acs.jpca.9b02927}},
doi = {{10.1021/acs.jpca.9b02927}},
volume = {{123}},
year = {{2019}},
}