Nitrile Substituents at the Conjugated Dipyridophenazine Moiety as Infrared Redox Markers in Electrochemically Reduced Heteroleptic Ru(II) Polypyridyl Complexes
Ruthenium(II) complexes [Ru(tap) (NN)] (tap = 1,4,5,8-tetraazaphenanthrene, NN = 11-cyano-dipyrido[3,2- :2',3'- ]phenazine (11-CN-dppz) and 11,12-dicyano-dipyrido[3,2- :2',3'- ]phenazine (11,12-CN-dppz)) feature the C≡N groups as infrared (IR)-active redox markers. They were stud...
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| Vydané v: | Inorganic chemistry Ročník 63; číslo 5; s. 2460 |
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| Hlavní autori: | , , , |
| Médium: | Journal Article |
| Jazyk: | English |
| Vydavateľské údaje: |
United States
05.02.2024
|
| ISSN: | 1520-510X, 1520-510X |
| On-line prístup: | Zistit podrobnosti o prístupe |
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| Shrnutí: | Ruthenium(II) complexes [Ru(tap)
(NN)]
(tap = 1,4,5,8-tetraazaphenanthrene, NN = 11-cyano-dipyrido[3,2-
:2',3'-
]phenazine (11-CN-dppz) and 11,12-dicyano-dipyrido[3,2-
:2',3'-
]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)
(11,12-CN-dppz)]
, 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 ν
(C≡N) modes by -18/-28 cm
, accompanied by a 4-fold enhancement of the ν
(C≡N) intensity, comparably with reference data for free 11,12-CN-dppz. The first tap-based reduction of spin-doublet [Ru(tap)
(11,12-CN-dppz)]
to spin-triplet [Ru(tap)
(11,12-CN-dppz)] at R2 decreased ν(C≡N) by merely -2 cm
, while the intensity enhancement reached an overall factor of 8. Comparably, a red shift of ν(C≡N) by -27 cm
resulted from the 1e
reduction of [Ru(tap)
(11-CN-dppz)]
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
and increased the absorbance by overall factors of 6.5 and 8, respectively. |
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| Bibliografia: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
| ISSN: | 1520-510X 1520-510X |
| DOI: | 10.1021/acs.inorgchem.3c03484 |