Nitrile Substituents at the Conjugated Dipyridophenazine Moiety as Infrared Redox Markers in Electrochemically Reduced Heteroleptic Ru(II) Polypyridyl Complexes

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Nitrile Substituents at the Conjugated Dipyridophenazine Moiety as Infrared Redox Markers in Electrochemically Reduced Heteroleptic Ru(II) Polypyridyl Complexes

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Nitrile Substituents at the Conjugated Dipyridophenazine Moiety as Infrared Redox Markers in Electrochemically Reduced Heteroleptic Ru(II) Polypyridyl Complexes

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10405 - Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis)

Projekt

<a href="/cs/project/GN23-05760O" target="_blank" >GN23-05760O: Redoxní a fotochemické vlastnosti polypyridylových biosenzorů</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2024

Kód důvěrnosti údajů

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

Název periodika

INORGANIC CHEMISTRY

ISSN

0020-1669

e-ISSN

1520-510X

Svazek periodika

63

Číslo periodika v rámci svazku

5

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

10

Strana od-do

2460-2469

Kód UT WoS článku

001158190100001

EID výsledku v databázi Scopus

2-s2.0-85184344362