title: Dual Emission of a Novel (P,N) Re(I) Complex: A Computational and Experimental Study on [P,N-{(C6H5)2(C5H4N)P}Re(CO)3Br].
abstract: The spectroscopic, electrochemical, and photophysical properties of the new complex [P,N-{(C6H5)2(C5H4N)P}Re(CO)3Br] are reported. The UV-vis spectrum in dichloromethane shows an absorption maximum centered at 315 nm and a shoulder at 350 nm. These absorption bands have been characterized to have MLCT character. Excitation at both wavelengths (maximum and shoulder) leads to an emission band centered at 550 nm. Cyclic voltammetry experiments show two ill-defined irreversible oxidation waves around +1.50 and 1.80 V that are assigned to Re(I)/Re(II) and Re(II)/Re(III) couples whereas an irreversible reduction signal centered at -1.80 V is likewise assigned to a ligand reduction process. These results support the proposal of the MLCT nature of the states implied by the emission of the complex. The luminescent decay fits to a biexponential function, where the lifetimes and emission quantum yields are dependent on the solvent polarity. DFT calculations suggest that dπ → π*pyridine and dπ → π*phenyl excited states may account for the existence of two decay lifetimes.
authors: †Departamento de Ciencias Químicas, Facultad de Ciencias Exactas, Universidad Andres Bello, Quillota 980, Viña del Mar, Valparaíso, Chile.
authors: Nancy
authors: N
authors: Pizarro
authors: †Departamento de Ciencias Químicas, Facultad de Ciencias Exactas, Universidad Andres Bello, Quillota 980, Viña del Mar, Valparaíso, Chile.
authors: Mario
authors: M
authors: Duque
authors: †Departamento de Ciencias Químicas, Facultad de Ciencias Exactas, Universidad Andres Bello, Quillota 980, Viña del Mar, Valparaíso, Chile.
authors: Eduardo
authors: E
authors: Chamorro
authors: ‡Institut Quimic de Sarrià, Universitat Ramon Llull, Via Augusta, 390, 08017 Barcelona, Spain.
authors: Santi
authors: S
authors: Nonell
authors: §Departamento de Ciencia de Los Materiales, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Av. Tupper 2069, Santiago, Chile.|⊥Centro para el Desarrollo de la Nanociencia y la Nanotecnología, CEDENNA, Universidad de Santiago de Chile, Avda. Ecuador 3493, Estación Central, Santiago, Chile.
authors: Jorge
authors: J
authors: Manzur
authors: ∥Facultad de Ciencias Químicas y Farmacéuticas, Departamento de Química Orgánica y Fisicoquímica, Universidad de Chile, Santos Dumont 964, Independencia, Chile.
authors: Julio R
authors: JR
authors: de la Fuente
authors: ∥Facultad de Ciencias Químicas y Farmacéuticas, Departamento de Química Orgánica y Fisicoquímica, Universidad de Chile, Santos Dumont 964, Independencia, Chile.
authors: Germán
authors: G
authors: Günther
authors: †Departamento de Ciencias Químicas, Facultad de Ciencias Exactas, Universidad Andres Bello, Quillota 980, Viña del Mar, Valparaíso, Chile.
authors: Marjorie
authors: M
authors: Cepeda-Plaza
authors: †Departamento de Ciencias Químicas, Facultad de Ciencias Exactas, Universidad Andres Bello, Quillota 980, Viña del Mar, Valparaíso, Chile.|⊥Centro para el Desarrollo de la Nanociencia y la Nanotecnología, CEDENNA, Universidad de Santiago de Chile, Avda. Ecuador 3493, Estación Central, Santiago, Chile.
authors: Andrés
authors: A
authors: Vega