Influence of the Halogen Ligand on the Near UV/Visible Spectrum of [Ru(X) (Me)(CO)2(alpha-diimine)] (X=Cl, I; alpha-diimine=Me-DAB, iPr-DAB; DAB=1,4-diaza-1,3-butadiene): An ab initio and TD-DFT Analysis

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F04%3A00107648" target="_blank" >RIV/61388955:_____/04:00107648 - isvavai.cz</a>

Result on the web

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DOI - Digital Object Identifier

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Result language

angličtina

Original language name

Influence of the Halogen Ligand on the Near UV/Visible Spectrum of [Ru(X) (Me)(CO)2(alpha-diimine)] (X=Cl, I; alpha-diimine=Me-DAB, iPr-DAB; DAB=1,4-diaza-1,3-butadiene): An ab initio and TD-DFT Analysis

Original language description

The near-UV/visible electronic spectroscopy of [Ru(X)(Me)(CO)2(iPr-DAB)] (X = Cl or I; iPr-DAB = N,N''-di-isoPropyl-1,4-diaza-1,3-butadiene) is investigated through CASSCF / CASPT2 and TD-DFT calculations on the model complexes [Ru(X)(Me)(CO)2(Me-DAB)] (X = Cl or I). Convergence of the calculated transition energies of the low-lying Metal-to-Ligand-Charge-Transfer (MLCT), X-to-Ligand-Charge-Transfer (XLCT, X halide ligand) or Sigma-Bond-to-Ligand-Charge-Transfer (SBLCT) to experimental values is analysed for both methods. - The previous formulation was unclear but I am not sure if you mean this. On the basis of these accurate calculations it is shown that, whereas the lowest singlet state can be assigned to a nearly pure XLCT state in [Ru(I)(Me)(CO)2(Me-DAB)], its character is mainly MLCT in [Ru(Cl)(Me)(CO)2(Me-DAB)]. These results are in agreement with time-resolved emission, IR absorption and resonance Raman experimental data.

Czech name

Vliv halogenového ligandu na blízké UV/Vis spektrum [Ru(X) (Me)(CO)2(alfa-diimine)] (X=Cl, I;alfa-diimine=Me-DAB, iPr-DAB; DAB=1,4-diaza-1,3-butadiene): Ab initio a TD-DFT analýza

Czech description

UV/Vis spektra [Ru(X)(Me)(CO)2(iPr-DAB)] (X = Cl nebo I; iPr-DAB = N,N'-di-isoPropyl-1,4-diaza-1,3-butadiene) komplexů byla interpretována pomocí CASSCF / CASPT2 a TD-DFT výpočtů na modelových komplexech [Ru(X)(Me)(CO)2(Me-DAB)] (X = Cl or I). Konvergence vypočtených nízko ležících přechodů přenosu náboje kov - ligand (MLCT) a X - ligand (XLCT, X halogenidový ligand) či sigma - vazba ? ligand (SBLCT) k experimentální hodnotám je analyzována pro obě metody. Výsledky teoretické studie jsou v souladu s časově rozlišenou emisní, IR a resonanční Ramanovou spektroskopií těchto sloučenin.

Type

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

CEP classification

CF - Physical chemistry and theoretical chemistry

OECD FORD branch

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Project

<a href="/en/project/1P04OCD14.20" target="_blank" >1P04OCD14.20: Oganometallic and Metallo-organic Building Blocks for Photonic Materials</a><br>

Continuities

Z - Vyzkumny zamer (s odkazem do CEZ)

Publication year

2004

Confidentiality

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

Name of the periodical

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

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Volume of the periodical

43

Issue of the periodical within the volume

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Country of publishing house

US - UNITED STATES

Number of pages

8

Pages from-to

7978-7985

UT code for WoS article

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EID of the result in the Scopus database

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