Nitrile Substituents at the Conjugated Dipyridophenazine Moiety as Infrared Redox Markers in Electrochemically Reduced Heteroleptic Ru(II) Polypyridyl Complexes
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F24%3A43928687" target="_blank" >RIV/60461373:22310/24:43928687 - isvavai.cz</a>
Result on the web
<a href="https://pubs.acs.org/doi/full/10.1021/acs.inorgchem.3c03484" target="_blank" >https://pubs.acs.org/doi/full/10.1021/acs.inorgchem.3c03484</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.inorgchem.3c03484" target="_blank" >10.1021/acs.inorgchem.3c03484</a>
Alternative languages
Result language
angličtina
Original language name
Nitrile Substituents at the Conjugated Dipyridophenazine Moiety as Infrared Redox Markers in Electrochemically Reduced Heteroleptic Ru(II) Polypyridyl Complexes
Original language description
Ruthenium(II) complexes [Ru(tap)2(NN)]2+ (tap = 1,4,5,8-tetraazaphenanthrene, NN = 11-cyano-dipyrido[3,2-a:2′,3′-c]phenazine (11-CN-dppz) and 11,12-dicyano-dipyrido[3,2-a:2′,3′-c]phenazine (11,12-CN-dppz)) feature the C≡N groups as infrared (IR)-active redox markers. They were studied by cyclic voltammetry, UV–vis, and IR spectroelectrochemistry (SEC), and density functional theory calculations to assign the four 1e– reduction waves R1–R4 observed in dichloromethane. Generally, the NN ligands are reduced first (R1). For [Ru(tap)2(11,12-CN-dppz)]2+, R1 is sufficiently separated from R2 and delocalized over both tap ligands. Accordingly, IR SEC conducted at R1 shows a large red shift of the νs,as(C≡N) modes by −18/–28 cm–1, accompanied by a 4-fold enhancement of the νs(C≡N) intensity, comparably with reference data for free 11,12-CN-dppz. The first tap-based reduction of spin-doublet [Ru(tap)2(11,12-CN-dppz)]+ to spin-triplet [Ru(tap)2(11,12-CN-dppz)] at R2 decreased ν(C≡N) by merely −2 cm–1, while the intensity enhancement reached an overall factor of 8. Comparably, a red shift of ν(C≡N) by −27 cm–1 resulted from the 1e– reduction of [Ru(tap)2(11-CN-dppz)]2+ at R1 (poorly resolved from R2), and the intensity enhancement was roughly 3-fold. Concomitant 1e– reductions of the tap ligands (R2 and R3) caused only minor ν(C≡N) shifts of −3 cm–1 and increased the absorbance by overall factors of 6.5 and 8, respectively.
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
10405 - Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis)
Result continuities
Project
<a href="/en/project/GN23-05760O" target="_blank" >GN23-05760O: Redox and photochemical properties of polypyridyl-based biosensors</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2024
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
INORGANIC CHEMISTRY
ISSN
0020-1669
e-ISSN
1520-510X
Volume of the periodical
63
Issue of the periodical within the volume
5
Country of publishing house
US - UNITED STATES
Number of pages
10
Pages from-to
2460-2469
UT code for WoS article
001158190100001
EID of the result in the Scopus database
2-s2.0-85184344362