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)]

Result code in IS VaVaI

RIV/61388955:_____/05:00025814 - isvavai.cz

Result on the web

—

DOI - Digital Object Identifier

—

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.

Type

J_x - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

CEP classification

CG - Electrochemistry

OECD FORD branch

—

Project

1P05OC068: Control of functional behaviour of transition - metal compounds

Continuities

Z - Vyzkumny zamer (s odkazem do CEZ)

Publication year

2005

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Journal of Physical Chemistry. A

ISSN

1089-5639

e-ISSN

—

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

—

EID of the result in the Scopus database

—