2026-04-27T12:41:09Zhttps://uvadoc.uva.es/oai/request

oai:uvadoc.uva.es:10324/287192025-02-20T10:19:21Zcom_10324_28708com_10324_954com_10324_894col_10324_28709

Gómez Iglesias, Patricia Guyon, Fabrice Khatyr, Abderrahim Ulrich, Gilles Knorr, Michael Martín Álvarez, José Miguel Miguel San José, Daniel Villafañe González, Fernando 2018-02-27T12:31:16Z 2018-02-27T12:31:16Z 2015 Dalton Transactions, 2015, 44, 17516–17528 1477-9226 http://uvadoc.uva.es/handle/10324/28719 10.1039/c5dt02793d 17516 17528 Luminescent rhenium(I) tricarbonyl complexes with pyrazolylamidino ligands: photophysical, electrochemical, and computational studies 44 Producción Científica New pyrazolylamidino complexes fac-[ReCl(CO)3(NHvC(Me)pz*-κ2N,N)] (pz*H = pyrazole, pzH; 3,5-dimethylpyrazole, dmpzH; indazole, indzH) and fac-[ReBr(CO)3(NHvC(Ph)pz*-κ2N,N)] are synthesized via base-catalyzed coupling of the appropriate nitrile with pyrazole, or via metathesis by halide abstraction with AgBF4 from a bromido pyrazolylamidino complex and the subsequent addition of LiCl. In order to study both the influence of the substituents present at the pyrazolylamidino ligand, and that of the “sixth” ligand in the complex, photophysical, electrochemical, and computational studies have been carried out on this series and other complexes previously described by us, of the general formula fac-[ReL(CO)3(NHvC(R’)pz*-κ2N,N)]n+ (L = Cl, Br; R’ = Me, Ph, n = 0; or L = NCMe, dmpzH, indzH, R’ = Me, n = 1). All complexes exhibit phosphorescent decays from a prevalently 3MLCT excited state with quantum yields (Φ) in the range between 0.007 and 0.039, and long lifetimes (τ ∼ 8–1900 ns). The electrochemical study reveals irreversible reduction for all complexes. The oxidation of the neutral complexes was found to be irreversible due to halido-dissociation, whereas the cationic species display a reversible process implying the ReI/ReII couple. Density functional and time-dependent density functional theory (TD-DFT) calculations provide a reasonable trend for the values of emission energies in line with the experimental photophysical data, supporting the 3MLCT based character of the emissions. MINECO (Project CTQ2013-41067-P) application/pdf eng The Royal Society of Chemistry info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by-nc-nd/4.0/ The Royal Society of Chemistry Attribution-NonCommercial-NoDerivatives 4.0 International Rhenium(I) Tricarbonyl Pyrazolylamidino In situ synthesis phosphorescence electrochemistry computational studies Luminescent rhenium(I) tricarbonyl complexes with pyrazolylamidino ligands: photophysical, electrochemical, and computational studies info:eu-repo/semantics/article http://pubs.rsc.org/en/content/articlelanding/2015/dt/c5dt02793d#!divAbstract SI