LABORATORIO de FOTOLUMINISCENCIA

POTENTIAL USES OF RHENIUM COMPLEXES AS PHOTOSENSITIZERS, BACTERICIDES OR MOLECULAR PROBES: A PHOTOPHYSICAL AND PHOTOCHEMICAL STUDY

FONDECYT 1160749 PROYECTO EN DESARROLLO

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Publicaciones: M. Saldías, N. Pizarro, G. Günther, C. Sandoval-Altamirano, N. Guzmán, F. Palominos, A. Vega, “Electronic and Photophysical Properties of ReI(CO)3Br Complexes Modulated by Pyrazolyl–Pyridazine Ligands”, ACS Omega, 4(3): 4679−4690, 2019 N. Pizarro, M. Saldías, N. Guzmán, C. Sandoval-Altamirano, S. Kahlal, J.-Y. Saillard, J.-R. Hamon, A. Vega, "1IL and 3MLCT excited states modulated by H+: the structure and photophysical properties of [(2-bromo-5-(1H-pyrazol-1-yl)pyrazine)Re(CO)3Br]", New Journal of Chemistry 43: 2449-2457, 2019 N. Pizarro, G. Prado, M. Saldías, C. Sandoval-Altamirano, A. Vega, "The Effect of Pyrazolyl Substituents on the Photophysical and Photochemical Properties of Pyrazine Derivatives", Photochemistry and Photobiology 94(5): 845-852, 2018 Marianela Saldías, Jorge Manzur, María L. Gómez, Rodrigo E. Palacios, Julio De La Fuente, Germán Günther, Nancy Pizarro, Andrés Vega, “The Binuclear Dual Emitter [Br(CO)3Re(-P,N-L)2Re(CO)3Br] (L:3-Chloro-6-(4-Diphenyl)-Butoxypyridazine), A New Bridging P,N-Bidentate Ligand Coming From A Solvent Ring Opening”, Dalton Transactions 46(5): 1567-1576, 2017. Gaspar Prado, María Belén Ibañez, Alison Acosta, Eduardo Chamorro, Patricio Hermosilla-Ibáñez, Germán Günther, Nancy Pizarro, Andrés Vega, “Kinetics and Photophysical Behavior of the P,N-ReI Complex [P,N-{(C6H5)2(C5H4N)PRe(CO)3(O-O3SCF3)]: A Directly Coordinated (and Labile) Triflate”,Polyhedron, 137: 222–230, 2017.

Dr. Nancy Pizarro Urzua

PROPOSAL ABSTRACT:

Rhenium (I) tricarbonyl complexes present remarkable luminescent properties which have attracted much attention in last decades. The convenient and easy synthesis and later the possibility to rationally change the ligands, have allowed the development of a wide range of interesting and important applications, including their use as catalysts, molecular probes, light-emitting materials, nonlinear optical materials, binding or photocleavage of DNA, and radiopharmaceuticals. It has been established that following its excitation with UV-Vis light, rhenium complexes (such as tricarbonyl derivatives), mainly yield a triplet metal-to-ligand charge transfer excited state (³MLCT). The ³MLCT excited state formed can decay to the ground state by different paths, such as radiative and nonradiative processes or by a photochemical reaction to yield products. Additionally, in the presence of molecular oxygen, these complexes have the ability of generate singlet oxygen, O₂(¹D_g), by means of an energy transference process. This research project proposes the synthesis of rhenium tricarbonyl complexes and a detailed study of two aspects comparatively less considered of the photo-behavior of them: its ability to generate singlet oxygen and the products they produce after irradiation, in order to explore their applications in photodynamic therapy or as molecular probes. Classical N,N ligands and hybrid P,N ligands will be considered, since we already information about their photophysical properties. Finally, the behavior of the rhenium complexes or some tailored derivative will be studied in bio-mimicking conditions.