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Different manifestations of enhanced π-acceptor ligation at every redox level of [Os(9-OP)L2]n, n = 2+, +, 0, − (9-OP− = 9-oxidophenalenone and L = bpy or pap)
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SYSNO ASEP 0467828 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Different manifestations of enhanced π-acceptor ligation at every redox level of [Os(9-OP)L2]n, n = 2+, +, 0, − (9-OP− = 9-oxidophenalenone and L = bpy or pap) Tvůrce(i) Hazari, A. S. (IN)
Paretzki, A. (DE)
Fiedler, Jan (UFCH-W) RID, ORCID
Záliš, Stanislav (UFCH-W) RID, ORCID
Kaim, W. (DE)
Lahiri, G. K. (IN)Zdroj.dok. Dalton Transactions. - : Royal Society of Chemistry - ISSN 1477-9226
Roč. 45, č. 45 (2016), s. 18241-18251Poč.str. 11 s. Jazyk dok. eng - angličtina Země vyd. GB - Velká Británie Klíč. slova Spectroelectrochemistry ; Redox reactions ; Ruthenium Vědní obor RIV CG - Elektrochemie CEP LD14129 GA MŠMT - Ministerstvo školství, mládeže a tělovýchovy Způsob publikování Open access Institucionální podpora UFCH-W - RVO:61388955 UT WOS 000388368600028 EID SCOPUS 84995785357 DOI https://doi.org/10.1039/c6dt03764j Anotace The title complexes were isolated as structurally characterised compounds [Os-II(9-OP)L-2]ClO4, L = 2,2'-bipyridine (bpy) or 2-phenylazopyridine (pap), and were compared with ruthenium analogues. A reversible one-electron oxidation and up to three reduction processes were observed by voltammetry (CV, DPV) and spectroelectrochemistry (UV-vis-NIR, partially EPR). Supporting calculations (DFT, TD-DFT) were used to assess the oxidation state combinations of the different redox active ligands and of the metal, revealing the effects of Os versus Ru exchange and of bpy versus pap acceptor ligation. Several unexpected consequences of these variations were observed for members of the new osmium-containing redox series. Remarkably, the EPR results exhibit a clear dichotomy between the complex ion [Os-III(9-OP-)( bpy)(2)](2+) and the radical species [Os-II(9-OP-)(pap)(2)](2+), which has not been similarly observed for the analogous [Ru-III(9-OP-)(L2)](2+) systems. This difference, unprecedented for 5d(n) systems, is attributed to the superior stabilisation of the Os-II state by the strongly pi-accepting pap ligands. The reduced forms [Os-II(9-OP-)(pap(-))(pap)] and [OsII(9-OP-)(pap(-))(2)](-) exhibit strong inter-ligand interactions, leading to spin isomers and electron hopping. Pracoviště Ústav fyzikální chemie J.Heyrovského Kontakt Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Rok sběru 2017
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