Replacement of 2,2''''-Bipyridine by 1,4-Diazabutadiene Acceptor Ligands: Why the Bathochromic Shift for [(N^N)IrCl(C5Me5)]+ Complexes but the Hypsochromic Shift for (N^N)Ir(C5Me5)?

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F03%3A54030171" target="_blank" >RIV/61388955:_____/03:54030171 - 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

Replacement of 2,2''''-Bipyridine by 1,4-Diazabutadiene Acceptor Ligands: Why the Bathochromic Shift for [(N^N)IrCl(C5Me5)]+ Complexes but the Hypsochromic Shift for (N^N)Ir(C5Me5)?

Original language description

Replacement of 2,2''-bipyridine (bpy) by substituted 1,4-diazabutadiene (R-DAB) alpha;-diimine ligands N^N leads to a substantial hypsochromic shift of about 0.8 eV for the long-wavelength absorption band in compounds (N^N)Ir(C5Me5) but to a bathochromicabsorption shift of about 0.4 eV for the complex ions [(N^N)IrCl(C5Me5)]+. DFT calculations on model complexes based on experimental (R-DAB compounds) and geometry-optimized structures (bpy systems) reveal that the low-energy transitions of the cationicchloro complexes are largely of ligandůto-ligand charge transfer character L''LCT (L = alpha-diimine, L'' = Cl) whereas the neutral compounds exhibit pí_pí* transitions between the considerably mixed metal d pí and alpha-diimine pí* orbitals. The much more pronounced metal-ligand orbital interaction for the R-DAB complexes causes the qualitatively different shifts on replacing the stronger basic bpy by the better pí-acceptors R-DAB.

Czech name

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Czech description

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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

Result was created during the realization of more than one project. More information in the Projects tab.

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>Z - Vyzkumny zamer (s odkazem do CEZ)

Publication year

2003

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

42

Issue of the periodical within the volume

N/A

Country of publishing house

US - UNITED STATES

Number of pages

7

Pages from-to

5185-5191

UT code for WoS article

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EID of the result in the Scopus database

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