Mixed Valency vs Radical Bridge Formulation in Symmetrically and Asymmetrically Ligated Diruthenium Complexes

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Mixed Valency vs Radical Bridge Formulation in Symmetrically and Asymmetrically Ligated Diruthenium Complexes

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Mixed Valency vs Radical Bridge Formulation in Symmetrically and Asymmetrically Ligated Diruthenium Complexes

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA21-05180S" target="_blank" >GA21-05180S: Přenos náboje v chromofor-proteinových komplexech tryptofanovými drahami</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2022

Kód důvěrnosti údajů

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

Název periodika

European Journal of Inorganic Chemistry

ISSN

1434-1948

e-ISSN

1099-0682

Svazek periodika

2022

Číslo periodika v rámci svazku

26

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

11

Strana od-do

e202200319

Kód UT WoS článku

000852060000001

EID výsledku v databázi Scopus

2-s2.0-85133067047