Excited states of nitro-polypyridine metal complexes and their ultrafast decay. Time-resolved IR absorption, spectroelectrochemistry, and TD-DFT calculations of fac-[Re(Cl)(CO)(3)(5-nitro-1,10-phenanthroline)]
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F05%3A00025814" target="_blank" >RIV/61388955:_____/05:00025814 - isvavai.cz</a>
Result on the web
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DOI - Digital Object Identifier
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Alternative languages
Result language
angličtina
Original language name
Excited states of nitro-polypyridine metal complexes and their ultrafast decay. Time-resolved IR absorption, spectroelectrochemistry, and TD-DFT calculations of fac-[Re(Cl)(CO)(3)(5-nitro-1,10-phenanthroline)]
Original language description
The lowest absorption band of fac-[Re(Cl)(CO)3(5-NO2-phen)] encompasses two close-lying MLCT transitions. The lower one is directed to LUMO, which is heavily localized on the NO2 group. The UV-vis absorption spectrum is well accounted for by TD-DFT (G03/PBEPBE1/CPCM), provided that the solvent, MeCN, is included in the calculations. Near-UV excitation of fac-[Re(Cl)(CO)3(5-NO2-phen)] populates a triplet metal to ligand charge-transfer excited state, 3(MLCT), that was characterized by picosecond time-resolved IR spectroscopy. Large positive shifts of the v(CO) bands upon excitation (+70 cm-1 for the A'(1) band) signify a very large charge separation between the Re(Cl)(CO)3 unit and the 5-NO2-phen ligand. Details of the excited-state character are revealed by TD-DFT calculated changes of electron density distribution.
Czech name
Excitované stavy nitro-polypyridinových komplexů s kovy a jejich ultra rychlý rozpad. Časově rozlišená IČ a absorpční spektroskopie, spektroelektrochemie a TD-DFT výpočty fac [Re(Cl)(CO)3(5-Nitro-1,10-phenanthrolin)]
Czech description
Nejnižší absorpční pás fac-[Re(Cl)(CO)3(5-NO2-phen)] obsahuje dva MLCT přechody, nižší z nich zahrnuje NO2 skupinu. UV-Vis absorpční spektrum je dobře popsáno TD-DFT výpočtem (G03/PBEPBE1/CPCM), za předpokladu, že ve výpočtu je uvažován vliv rozpouštědla. Excitace fac-[Re(Cl)(CO)3(5-NO2-phen)] v blízké UV oblasti populuje tripletní excitovaný stav přenosu náboje kov - ligand, 3MLCT, který byl charakterizován časově rozlišenou IČ spektroskopií. Experimentální v(CO) frekvence souhlasí DFT vypočtenými frekvencemi.
Classification
Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CG - Electrochemistry
OECD FORD branch
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Result continuities
Project
<a href="/en/project/1P05OC068" target="_blank" >1P05OC068: Control of functional behaviour of transition - metal compounds</a><br>
Continuities
Z - Vyzkumny zamer (s odkazem do CEZ)
Others
Publication year
2005
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
109
Issue of the periodical within the volume
28
Country of publishing house
US - UNITED STATES
Number of pages
7
Pages from-to
6147-6153
UT code for WoS article
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EID of the result in the Scopus database
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