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)
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F16%3A00467828" target="_blank" >RIV/61388955:_____/16:00467828 - isvavai.cz</a>
Result on the web
<a href="http://dx.doi.org/10.1039/c6dt03764j" target="_blank" >http://dx.doi.org/10.1039/c6dt03764j</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/c6dt03764j" target="_blank" >10.1039/c6dt03764j</a>
Alternative languages
Result language
angličtina
Original language name
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)
Original language description
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.
Czech name
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Czech description
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Classification
Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CG - Electrochemistry
OECD FORD branch
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Result continuities
Project
<a href="/en/project/LD14129" target="_blank" >LD14129: Structure and dynamics of excited and redox states of photocatalytic complexes</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2016
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Dalton Transactions
ISSN
1477-9226
e-ISSN
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Volume of the periodical
45
Issue of the periodical within the volume
45
Country of publishing house
GB - UNITED KINGDOM
Number of pages
11
Pages from-to
18241-18251
UT code for WoS article
000388368600028
EID of the result in the Scopus database
2-s2.0-84995785357