RT info:eu-repo/semantics/article
T1 Luminescent rhenium(I) tricarbonyl complexes with pyrazolylamidino ligands: photophysical, electrochemical, and computational studies
A1 Gómez Iglesias, Patricia
A1 Guyon, Fabrice
A1 Khatyr, Abderrahim
A1 Ulrich, Gilles
A1 Knorr, Michael
A1 Martín Álvarez, José Miguel
A1 Miguel San José, Daniel
A1 Villafañe González, Fernando
K1 Rhenium(I) Tricarbonyl
K1 Pyrazolylamidino
K1 In situ synthesis
K1 phosphorescence
K1 electrochemistry
K1 computational studies
AB 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.
PB The Royal Society of Chemistry
SN 1477-9226
YR 2015
FD 2015
LK http://uvadoc.uva.es/handle/10324/28719
UL http://uvadoc.uva.es/handle/10324/28719
LA eng
NO Dalton Transactions, 2015, 44, 17516–17528
NO Producción Científica
DS UVaDOC
RD 22-dic-2024