Journal article
Investigation of Vibrational Cooling in a Photoexcited Dichloro-Ruthenium Charge Transfer Complex Using Transient Electronic Absorption Spectroscopy
The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.129(9), pp.2265-2274
03/06/2025
DOI: 10.1021/acs.jpca.5c00367
PMCID: PMC11891904
PMID: 39993167
Appears in UI Libraries Support Open Access
Abstract
Vibrational cooling of molecules in excited electronic states is ubiquitous in photochemical reactions in solution but challenging to infer in time-resolved electronic absorption experiments. We report the ultrafast photophysics of
-dichlorobis(2,2'-bipyridine)ruthenium(II), Ru(bpy)
Cl
, a precursor molecule commonly utilized in synthetic modifications of a vast array of ruthenium complexes. Femtosecond time-resolved electronic absorption spectroscopy is used to track an ultrafast spectral narrowing of the excited-state absorptions at 475 nm (21,050 cm
) and 505 nm (19,800 cm
) due to the reduced ligand in the photoexcited molecular complex. These sharp features, which overlap with a broader ground-state bleach spanning 450 nm (22,220 cm
) to 600 nm (16,670 cm
), evolve rapidly with time constants of 16 ± 5, 15 ± 3, and 18 ± 2 ps, respectively, for ligand-centered (π → π*, 266 nm) and charge-transfer (t
→ π*, 400 and 550 nm) excitations and constitute a direct signature of picosecond vibrational cooling.
Details
- Title: Subtitle
- Investigation of Vibrational Cooling in a Photoexcited Dichloro-Ruthenium Charge Transfer Complex Using Transient Electronic Absorption Spectroscopy
- Creators
- Caleb H DeWitt - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, United StatesAustin D Heidbreder - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, United StatesGriffin W Hancock - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, United StatesAditi Bhattacherjee - University of Iowa
- Resource Type
- Journal article
- Publication Details
- The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.129(9), pp.2265-2274
- DOI
- 10.1021/acs.jpca.5c00367
- PMID
- 39993167
- PMCID
- PMC11891904
- NLM abbreviation
- J Phys Chem A
- ISSN
- 1089-5639
- eISSN
- 1520-5215
- Publisher
- American Chemical Society
- Grant note
- American Chemical Society Petroleum Research Fund: 66711-DNI6 ACS Petroleum Research Fund under Doctoral New Investigator Grant: 66711-DNI6 ACS PRFUniversity of IowaCollege of Liberal Arts and Sciences
This work was supported by the donors of ACS Petroleum Research Fund under Doctoral New Investigator Grant 66711-DNI6. A.B. served as Principal Investigator on ACS PRF 66711-DNI6 that provided support for C.H.D, A.D.H., and G.W.H. The authors gratefully acknowledge start-up funds provided by the University of Iowa, extended support from the College of Liberal Arts and Sciences, and building operations and maintenance of Iowa Advanced Technology Laboratories that enabled the design, construction and implementation of the experimental apparatus. This research was supported in part through computational resources (University of Iowa) and shared instrument facilities including instructional laboratories (Department of Chemistry, University of Iowa).
- Language
- English
- Electronic publication date
- 02/24/2025
- Date published
- 03/06/2025
- Academic Unit
- Chemistry
- Record Identifier
- 9984795378802771
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