RT info:eu-repo/semantics/article T1 (1,2-Azole)bis(bipyridyl)ruthenium(II) Complexes: Electrochemistry, Luminescent Properties, And Electro- And Photocatalysts for CO2 Reduction A1 Cuéllar González, Elena A1 Pastor, Laura A1 García-Herbosa, Gabriel A1 Nganga, John A1 Angeles-Boza, Alfredo M. A1 Diez de la Varga, Alberto A1 Torroba, Tomás A1 Martín-Alvarez, Jose M. A1 Miguel San José, Daniel A1 Villafañe González, Fernando AB New cis-(1,2-azole)-aquo bis(2,2′-bipyridyl)ruthenium(II) (1,2-azole (az*H) = pzH (pyrazole), dmpzH (3,5-dimethylpyrazole), and indzH (indazole)) complexes are synthesized via chlorido abstraction from cis-[Ru(bipy)2Cl(az*H)]OTf. The latter are obtained from cis-[Ru(bipy)2Cl2] after the subsequent coordination of the 1,2-azole. All the compounds are characterized by 1H, 13C, 15N NMR spectroscopy as well as IR spectroscopy. Two chlorido complexes (pzH and indzH) and two aquo complexes (indzH and dmpzH) are also characterized by X-ray diffraction. Photophysical and electrochemical studies were carried out on all the complexes. The photophysical data support the phosphorescence of the complexes. The electrochemical behavior of all the complexes in an Ar atmosphere indicate that the oxidation processes assigned to Ru(II) → Ru(III) occurs at higher potentials in the aquo complexes. The reduction processes under Ar lead to several waves, indicating that the complexes undergo successive electron-transfer reductions that are centered in the bipy ligands. The first electron reduction is reversible. The electrochemical behavior in CO2 media is consistent with CO2 electrocatalyzed reduction, where the values of the catalytic activity [icat(CO2)/ip(Ar)] ranged from 2.9 to 10.8. Controlled potential electrolysis of the chlorido and aquo complexes affords CO and formic acid, with the latter as the major product after 2 h. Photocatalytic experiments in MeCN with [Ru(bipy)3]Cl2 as the photosensitizer and TEOA as the electron donor, which were irradiated with >300 nm light for 24 h, led to CO and HCOOH as the main reduction products, achieving a combined turnover number (TONCO+HCOO–) as high as 107 for 2c after 24 h of irradiation. PB American Chemical Society SN 0020-1669 YR 2021 FD 2021 LK https://uvadoc.uva.es/handle/10324/65931 UL https://uvadoc.uva.es/handle/10324/65931 LA eng NO Inorganic Chemistry, 2021, vol. 60, n 2, p. 692–704 NO Producción Científica DS UVaDOC RD 12-jul-2024