Author, as appears in the article.: Karlin, K.D. Meyer, G.J. Neese, F. Zapata Rivera, J.E. Liakos, D.G. Saracini, C.
Department: Química Física i Inorgànica
Abstract: Irradiation of the copper(II)-superoxide synthetic complexes [(TMG 3tren)CuII(O2)]+ (1) and [(PV-TMPA)CuII(O2)]+ (2) with visible light resulted in direct photogeneration of O2 gas at low temperature (from -40 C to -70 C for 1 and from -125 to -135 C for 2) in 2-methyltetrahydrofuran (MeTHF) solvent. The yield of O2 release was wavelength dependent: ?exc = 436 nm, = 0.29 (for 1), = 0.11 (for 2), and ?exc = 683 nm, = 0.035 (for 1), = 0.078 (for 2), which was followed by fast O2-recombination with [(TMG3tren)Cu I]+ (3) and [(PV-TMPA)CuI]+ (4). Enthalpic barriers for O2 rebinding to the copper(I) center (~10 kJ mol-1) and for O2 dissociation from the superoxide compound 1 (45 kJ mol-1) were determined. TD-DFT studies, carried out for 1, support the experimental results confirming the dissociative character of the excited states formed upon blue- or red-light laser excitation.
Thematic Areas: Copper compounds
licence for use: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 0002-7863
Last page: 1263
Journal volume: 136
Papper version: info:eu-repo/semantics/submittedVersion
Link to the original source: http://pubs.acs.org/doi/abs/10.1021/ja4115314
Article's DOI: 10.1021/ja4115314
Entity: Universitat Rovira i Virgili.
Journal publication year: 2014
First page: 1260
Repositori URV