LIGANDOS CARBENO N-HETEROCICLICO EN LA ESTABILIZACION DE RADICALES DE PD(I) Y EN LA PREPARACION DE COMPLEJOS METALICOS HIDROSOLUBLES

PID2020-114637GB-I00

Nombre agencia financiadora Agencia Estatal de Investigación
Acrónimo agencia financiadora AEI
Programa Programa Estatal de Generación de Conocimiento y Fortalecimiento Científico y Tecnológico del Sistema de I+D+i
Subprograma Subprograma Estatal de Generación de Conocimiento
Convocatoria Proyectos I+D
Año convocatoria 2020
Unidad de gestión Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020
Centro beneficiario UNIVERSIDAD DE ALCALA
Identificador persistente http://dx.doi.org/10.13039/501100011033

Publicaciones

Found(s) 5 result(s)
Found(s) 1 page(s)

A Doublet State Palladium(I) N-Heterocyclic Carbene Complex as a Dopant and Stabilizer for Improved Photostability in Organic Solar Cells

e_Buah Biblioteca Digital Universidad de Alcalá
  • El Astal Quirós, Aliah
  • Carrarini, Valentina
  • Zarotti, Francesca
  • Rahman, Atiq Ur
  • Lledós, Agustí
  • García Yebra, María Cristina|||0000-0002-5545-5112
  • Jesús Alcañiz, Ernesto de|||0000-0001-8101-1358
  • Reale, Andrea
The effect of doublet state metalloradical complex in a solar cell inside the common active layer poly(3-hexylthiophene)/[6,6]-phenyl-C61-butyric acid methyl ester (P3HT/PC60BM) is explored. In this work, it is demonstrated that the role of the bis-[1,3-bis-(2,6-diisopropylphenyl)-4,5-dichloroimidazol-2-ylidene]palladium(I) hexafluoridophosphate dopant, [Pd(IPrCl)2][PF6], is crucial because the presence of a stable unpaired electron in the molecule significantly improves the optoelectronic performance of the device. We f the optimal concentration of this molecule in the active layer and demonstrate that the presence of this additive in the active layer helps to significantly improve the morphology of the device. The improvements in optoelectronic and morphological parameters are associated with a remarkable increase in photocurrent generation due to more favorable mechanisms of charge separation at the donor/acceptor (D/A) interfaces of the active layer and reduced recombinations. Moreover, the presence of this additive improves the stability of the unencapsulated solar cell against photochemical degradation produced by sunlight., European Union, Ministerio de Ciencia e Innovación




Pyridyl-triazole ligands enable in situ generation of a highly active dihydride iridium(III) complex for formic acid dehydrogenation

e_Buah Biblioteca Digital Universidad de Alcalá
  • Abán Alfaro, Miriam
  • Cuenca, J. Marco
  • Embid Cruces, Irene
  • Toro Molina, Alba de
  • Gómez Sal, Pilar|||0000-0002-9279-210X
  • Jesús Alcañiz, Ernesto de|||0000-0001-8101-1358
  • Valencia Calvo, Marta
  • García Yebra, María Cristina|||0000-0002-5545-5112
The reaction of [Cp*IrCl2]2 with 1-pyridyl-1,2,3-triazoles La-Ld in the presence of sodium triflate yielded the complexes [Cp*Ir(k2-NN)(Cl)][OTf] (1a?1d) in which the k2-NN ligand coordinates to iridium through the pyridyl nitrogen and the N2 nitrogen of the triazole ring, leaving the more basic N3 atom free. These complexes effectively catalyze the dehydrogenation of formic acid in the presence or absence of an external solvent, achieving turnover frequencies (TOFmax) of up to 10703 h-1 and producing a 1:1 mixture of hydrogen and carbon dioxide with no detectable carbon monoxide. The catalysts can be reused after a single reaction cycle, as they retain their activity. This retention of activity has allowed to reach a cumulative turnover number (TON) of 26876 after six reloading cycles of formic acid with catalyst 1d in the presence of sodium formate as a base. Kinetic and 1H NMR spectroscopy studies indicate that the active catalyst of the reaction is complex [Cp*Ir(CO)H2] (2), which was formed under the reaction conditions from precursors 1a-1d. Consequently, complexes 1a-1d act as stable precatalyst, avoiding the difficulties associated with handling the unstable complex 2. The reaction mechanism is likely to involve mono- and dihydride species. The decarboxylation of the coordinated formate is the rate-determining step at high formic acid concentrations, according to the kinetic profiles and kinetic isotope effect (KIE) values obtained, Ministerio de Ciencia, Innovación y Universidades, European Union




Reversible Single-Electron-Transfer to Oxygen in a Stable N-Heterocyclic Carbene Palladium(I) Metalloradical

e_Buah Biblioteca Digital Universidad de Alcalá
  • Dragomir-Maties, Georgiana
  • Gómez Sal, Pilar|||0000-0002-9279-210X
  • García Yebra, María Cristina|||0000-0002-5545-5112
  • Andrés Herranz, Román|||0000-0002-6215-8116
  • Jesús Alcañiz, Ernesto de|||0000-0001-8101-1358
The chemical and electrochemical one-electron oxidation of [Pd(IPr)2] (1) leads to the formation of mononuclear palladium(I) complex [Pd(IPr)2][PF6] (2). This bench-stable metalloradical has been fully characterized and its structure confirmed by X-ray diffraction analysis. EPR and DFT studies confirm the localization of the unpaired electron onto the metal center. Low temperature NMR and EPR measurements reveal the ability of complex 2 to reversibly coordinate and reduce the dioxygen molecule, leading to the formation of a three-coordinate complex, [PdII(IPr)2(?1-O2)]+ (4), in which the unpaired electron has beentransferred to the superoxido ligand., Ministerio de Ciencia e Innovación, Universidad de Alcalá




Pyridyl-triazole ligands enable in situ generation of a highly active dihydride iridium(III) complex for formic acid dehydrogenation

e-cienciaDatos, Repositorio de Datos del Consorcio Madroño
  • García Yebra, Cristina
  • Valencia Calvo, Marta
  • Jesús Alcañiz, Ernesto de
  • Abán Alfaro, Miriam
  • Embid Cruces, Irene
  • Toro Molina, Alba de
  • Cuenca, J. Marco
  • Gómez Sal, Pilar
Datos correspondientes a medidas de difracción de rayos X




Reversible Single-Electron-Transfer to Oxygen in a Stable N‑Heterocyclic Carbene Palladium(I) Metalloradical

e-cienciaDatos, Repositorio de Datos del Consorcio Madroño
  • García Yebra, Cristina
  • Andrés Herranz, Román
  • Jesús Alcañiz, Ernesto de
  • Dragomir-Maties, Georgiana
  • Gómez Sal, Pilar
Datos correspondientes a medidas de difracción de rayos X