Sistemas Luminiscentes Ciclometalados de Pt e Ir con Cromóforos 2-Arilbenzotiazol: Aplicaciones Biológicas y Fotocatalíticas

Coordination transition metal complexes with conjugated aromatic ligands have been an area of interest in recent years due to their wide variety of applications associated with their interesting optoelectronic properties and the great versatility of modulation depending on the environment and the nature of the coligands. In this context, this PhD Thesis focuses on the synthesis, characterization, study of the properties and possible biological and photocatalytic applications of new luminescent systems based on cyclometalated Pt and Ir complexes with the 2-arylbenzothiazole unit with different coligands. Two series of related cyclometalated Pt(II) complexes and Ir(III) complexes with 2-phenylbenzothiazole (pbt) as chromophore and featuring chelating deprotonated diphenylphosphines functionalized (acid groups) as coligands, have been prepared and their optical and electronic properties have also been compared and examined by theoretical TD- DFT calculations. This study suggest that phosphine ligands exert scarce or no influence on the excited states and that the Pt(II) compounds exhibit greater metallic contribution in the electronic transitions involved in their optical properties giving rise higher quantum yields, compared to those of Ir(III). On the other hand, two families of Pt(II) compounds featuring picolinate as coligands, which exhibitidistintic intermolecular interactions, have been prepared. In these complexes, the variation of the substituent in the picolinate chelate ligand and the crystallization solvent originate different types of solid phases with distinct optical properties, including mechanochromic behavior. Furthermore, the Me2N-pbt complexes show dual emissions, singlet oxygen generation and antiproliferative ability. This latter has been studied against breast and lung cancer tumour cell lines (MDA-MB-231 and A549) and non-tumour breast cell line (MCF10A) in the dark and under photoinduction conditions, in collaboration with a group of the Institute of Molecular Chemistry of the Sorbonne University. In adition, a series of Pt(II) mononuclear compounds bearing pbt and pyrazole ligands and binuclear Pt(II)-Pt(II) derivatives with pbt and Me2N-pbt and bridging pyrazolate ligands, have been also synthetized. The bimetallic compounds show a remarkable tendency to oxidize, giving rise to Pt(III)-Pt(III) binuclear derivatives with a formal Pt-Pt covalent bond. The Pt(II)-Pt(II) binuclear derivative featuring the Me2N-pbt cyclometalated unit shows a dual Fluorescence and Phosphorescence emision, depending on the excitation wavelength. Furthermore, this compound shows singlet oxygen generation capacity which has been analyzed and evaluated in the photooxidation process of p- bromothioanisole to methyl-p-bromophenylsulfoxide with blue light. Finally, the synthesis of a series of heteroleptic pentafluorophenyl-bis(2-phenylbenzothiazole) derivatives of Pt(IV) bearing N-donor and trifluoroacetate ligands and of the binuclear complex with bpyb as bridging ligand has been carried out. The variation of the ligand located in the trans position to the metalated carbon has allowed us to study its influence on the optical properties (absorption and emission) and lipophilicity, this latter closely related to the permeability and metabolism of the molecules in cells. The cytotoxic activity and interaction with DNA of some selected derivatives has also been evaluated in collaboration with a group of the CIBIR.

Grantor dc:publisher

Universidad de La Rioja (España)

Year dc:date

2024

Author dc:creator

• Gómez de Segura Zorzano, David

Contributors dc:contributor

• Moreno García, María Teresa (Universidad de La Rioja)
• Lalinde Peña, Elena (Universidad de La Rioja)

Statement dc:rights

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Language dc:language

spa

Repository record dc:identifier

https://dialnet.unirioja.es/servlet/oaites?codigo=348365

OAI identifier oai:identifier

oai:dialnet.unirioja.es:TES0000023161