Vibrational Relaxation and Redistribution Dynamics in Ruthenium(II) Polypyridyl-Based Charge-Transfer Excited States: A Combined Ultrafast Electronic and Infrared Absorption Study
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F18%3A00494623" target="_blank" >RIV/61388955:_____/18:00494623 - isvavai.cz</a>
Result on the web
<a href="http://dx.doi.org/10.1021/acs.jpca.8b06197" target="_blank" >http://dx.doi.org/10.1021/acs.jpca.8b06197</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.jpca.8b06197" target="_blank" >10.1021/acs.jpca.8b06197</a>
Alternative languages
Result language
angličtina
Original language name
Vibrational Relaxation and Redistribution Dynamics in Ruthenium(II) Polypyridyl-Based Charge-Transfer Excited States: A Combined Ultrafast Electronic and Infrared Absorption Study
Original language description
Ultrafast time-resolved electronic and infrared absorption measurements have been carried out on a series of Ru(II) polypyridyl complexes in an effort to delineate the dynamics of vibrational relaxation in this class of charge transfer chromophores. Time-dependent density functional theory calculations performed on compounds of the form [Ru(CN-Me-bpy)x(bpy)3-x]2+(x = 1-3 for compounds 1-3, respectively, where CN-Me-bpy is 4,4′-dicyano-5,5′-dimethyl-2,2′-bipyridine and bpy is 2,2′-bipyridine) reveal features in their charge-transfer absorption envelopes that allow for selective excitation of the Ru(II)-(CN-Me-bpy) moiety, the lowest-energy MLCT state(s) in each compound of the series. Changes in band shape and amplitude of the time-resolved differential electronic absorption data are ascribed to vibrational cooling in the CN-Me-bpy-localized3MLCT state with a time constant of 8 ± 3 ps in all three compounds. This conclusion was corroborated by picosecond time-resolved infrared absorption measurements, sharpening of the CN stretch in the3MLCT excited state was observed with a time constant of 3.0 ± 1.5 ps in all three members of the series. Electronic absorption data acquired at higher temporal resolution revealed spectral modulation over the first 2 ps occurring with a time constant of Γ = 170 ± 50 fs, in compound 1, corresponding effects are significantly attenuated in compound 2 and virtually absent in compound 3. We assign this feature to intramolecular vibrational redistribution (IVR) within the3MLCT state and represents a rare example of this process being identified from time-resolved electronic absorption data for this important class of chromophores.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/GA17-01137S" target="_blank" >GA17-01137S: Electron Transfer in (Bio)Molecular Systems: Time-Resolved Vibrational Spectroscopy and Theory</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2018
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Physical Chemistry A
ISSN
1089-5639
e-ISSN
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Volume of the periodical
122
Issue of the periodical within the volume
40
Country of publishing house
US - UNITED STATES
Number of pages
13
Pages from-to
7941-7953
UT code for WoS article
000447471400002
EID of the result in the Scopus database
2-s2.0-85054281438