Mixed Valency vs Radical Bridge Formulation in Symmetrically and Asymmetrically Ligated Diruthenium Complexes
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F22%3A00561665" target="_blank" >RIV/61388955:_____/22:00561665 - isvavai.cz</a>
Result on the web
<a href="https://hdl.handle.net/11104/0334188" target="_blank" >https://hdl.handle.net/11104/0334188</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/ejic.202200319" target="_blank" >10.1002/ejic.202200319</a>
Alternative languages
Result language
angličtina
Original language name
Mixed Valency vs Radical Bridge Formulation in Symmetrically and Asymmetrically Ligated Diruthenium Complexes
Original language description
The asymmetrical dinuclear [{(trpy*)Ru}(2)(mu-adc-Salph)Cl](PF6) 1(PF6), trpy*=4,4´,4´´-tri-tert-butyl-2,6,2´,6´´-terpyridine, adc-Salph=1-benzoyl-2-salicyloylhydrazido(3-), and the related symmetrical dinuclear [{Cl(trpy*)Ru}(2)(mu,eta(2) : eta(2)-adc-Ph)](PF6) 2(PF6), adc-Ph=1,2-bis(benzoyl)hydrazido(2-), were synthesized and structurally characterized. Both paramagnetic compounds were compared with the previously reported symmetrical [{(trpy*)Ru}(2)(mu,eta(3) : eta(3)-adc-Sal)](PF6) 3(PF6) containing the bis-tridentate bridge 1,2-bis(salicyloyl)hydrazido(4-). Molecular structures and magnetic resonance features (H-1 NMR, EPR) indicate spin density distribution over the metal(s) and the bridging ligand. Reversible one-electron reduction and oxidation were possible in all instances yielding comproportionation constants K-c of about 10(9) for the paramagnetic intermediates 1(+)-3(+). Structural results, spin density distribution and UV-Vis-NIR spectroelectrochemistry were analyzed for 1(+) with the help of TD-DFT calculations for a model compound (tert-Bu> Me). Intense absorptions around lambda(max)=1450-1650 nm for the cations were assigned to mixed metal/ligand transitions with significant inter-valence charge transfer (IVCT) character. For both the symmetrical and asymmetrical arrangements the cationic intermediates can be described as considerably mixed metal/ligand systems.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/GA21-05180S" target="_blank" >GA21-05180S: Driving Charge Transport in Chromophore-Protein Complexes through Tryptophan Pathways</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2022
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
European Journal of Inorganic Chemistry
ISSN
1434-1948
e-ISSN
1099-0682
Volume of the periodical
2022
Issue of the periodical within the volume
26
Country of publishing house
DE - GERMANY
Number of pages
11
Pages from-to
e202200319
UT code for WoS article
000852060000001
EID of the result in the Scopus database
2-s2.0-85133067047