Excitation-Wavelength-Dependent Photophysics of d8d8 Di-isocyanide Complexes
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F22%3A00549946" target="_blank" >RIV/61388955:_____/22:00549946 - isvavai.cz</a>
Alternative codes found
RIV/60461373:22310/22:43924236
Result on the web
<a href="http://hdl.handle.net/11104/0325841" target="_blank" >http://hdl.handle.net/11104/0325841</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.inorgchem.1c02645" target="_blank" >10.1021/acs.inorgchem.1c02645</a>
Alternative languages
Result language
angličtina
Original language name
Excitation-Wavelength-Dependent Photophysics of d8d8 Di-isocyanide Complexes
Original language description
Binuclear Rh(I) and Ir(I) TMB (2,5-dimethyl-2,5-diisocyanohexane) and dimen (1,8-diisocyanomenthane) complexes possess dσ*pσ and dπpσ singlet and triplet excited states that can be selectively excited in the visible and UV spectral regions. Using perturbational spin–orbit TDDFT, we unraveled the detailed character and spin mixing of these electronic transitions and found that delocalization of pσ and dπ orbitals over C≡N– groups makes C≡N stretching vibrations sensitive reporters of electron density and structural changes upon electronic excitation. Picosecond time-resolved infrared spectra measured after visible light, 375 nm, and 316 nm excitation revealed excitation-wavelength-dependent deactivation cascades. Visible light irradiation prepares the 1dσ*pσ state that, after one or two (sub)picosecond relaxation steps, undergoes 70–1300 ps intersystem crossing to 3dσ*pσ, which is faster for the more flexible dimen complexes. UV-excited 1,3dπpσ states decay with (sub)picosecond kinetics through a manifold of high-lying triplet and mixed-spin states to 3dσ*pσ with lifetimes in the range of 6–19 ps (316 nm) and 19–43 ps (375 nm, Ir only), bypassing 1dσ*pσ. Most excited-state conversion and some relaxation steps are accompanied by direct decay to the ground state that is especially pronounced for the most flexible long/eclipsed Rh(dimen) conformer.
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
—
OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2022
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Inorganic Chemistry
ISSN
0020-1669
e-ISSN
1520-510X
Volume of the periodical
61
Issue of the periodical within the volume
6
Country of publishing house
US - UNITED STATES
Number of pages
15
Pages from-to
2745-2759
UT code for WoS article
000732030300001
EID of the result in the Scopus database
2-s2.0-85121641950