Evidence for the dimer-of-(mixed-valent dimers) configuration in tetranuclear {(mu(4)-TCNX)[Ru(NH3)(5)](4)}(8+), TCNX = TCNE and TCNQ, from DFT calculations

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F09%3A00335779" target="_blank" >RIV/61388955:_____/09:00335779 - 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

Evidence for the dimer-of-(mixed-valent dimers) configuration in tetranuclear {(mu(4)-TCNX)[Ru(NH3)(5)](4)}(8+), TCNX = TCNE and TCNQ, from DFT calculations

Original language description

DFT calculations of the complex ions {(mu(4)-TCNX)[Ru(NH3)(5)](4)}(8+), TCNX = tetracyanoethene (TCNE) and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ), yield triplet state energy minimum structures with nonplanar bridging ligands. The calculated C-C bonddistances and twist angles confirm considerable metal-to-ligand electron transfer from the metal centers to the TCNE and TCNQ bridges in the lowest triplet and singlet states. The resulting situation, involving a weak interaction between two strongly coupled malonodinitrilato-bridged (RuRu2.5)-Ru-2.5 entities (Class III), agrees with experimental results; the near-orthogonality found for the ground states of the molecular ions explains the observed magnetic exchange coupling between two S = 1/2 sites, the 1,258 cm(-1) absorption in the IR spectrum of the TCNE complex, and the reversible two-electron oxidation. The nitrile stretching frequency shifts were reasonably reproduced by the calculations.

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

CG - Electrochemistry

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

2009

Confidentiality

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

Name of the periodical

Monatshefte fur Chemie

ISSN

0026-9247

e-ISSN

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Volume of the periodical

140

Issue of the periodical within the volume

7

Country of publishing house

AT - AUSTRIA

Number of pages

9

Pages from-to

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UT code for WoS article

000266926500005

EID of the result in the Scopus database

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