The aqueous photochemistry of cis-[Ru(bpy)2(CO)Cl]+ (1) was investigated at 310 K and under visible light (white) irradiation by NMR and ESI-HR-MS. Complex 1 releases a Cl ligand, coordinates a solvent molecule, and forms the complex cis- [Ru(bpy)2(CO)(H2O)]2+ (2). Also, irradiation experiments were performed in the presence of the nucleobase derivatives 9-ethylguanine (9-EtG) and 9-ethyladenine (9-EtA). Formation of Ru-9-EtG adducts was observed after 3 h irradiation by NMR and HR-MS, while only very small amounts of a Ru-9-EtA adduct could be detected by HR-MS. Solution structural data were obtained by X-ray absorption spectroscopy (XAS) for both 1 and 2. EXAFS gave a Ru-Cl distance of 2.416(7) A for 1 and a Ru-OH2O distance of 2.102(6) A for 2. DFT and TDDFT were employed to study the photophysical and photochemical properties of 1. Calculations show that dissociative metal-centered states can be related to the light-induced release of a Cl ligand and subsequent coordination of a solvent molecule. The compound showed no antiproliferative activity in three human carcinoma cell lines (lung, bladder, pancreas) under the testing conditions, either with or without irradiation with UV light.

EXAFS, DFT, light-induced nucleobase binding, and cytotoxicity of the photoactive complex cis-[Ru(bpy)2(CO)Cl]+

RUIU, TIZIANA;GARINO, Claudio;BARDELLI, Fabrizio;GIANOLIO, DIEGO;LAMBERTI, Carlo;GOBETTO, Roberto;
2010

Abstract

The aqueous photochemistry of cis-[Ru(bpy)2(CO)Cl]+ (1) was investigated at 310 K and under visible light (white) irradiation by NMR and ESI-HR-MS. Complex 1 releases a Cl ligand, coordinates a solvent molecule, and forms the complex cis- [Ru(bpy)2(CO)(H2O)]2+ (2). Also, irradiation experiments were performed in the presence of the nucleobase derivatives 9-ethylguanine (9-EtG) and 9-ethyladenine (9-EtA). Formation of Ru-9-EtG adducts was observed after 3 h irradiation by NMR and HR-MS, while only very small amounts of a Ru-9-EtA adduct could be detected by HR-MS. Solution structural data were obtained by X-ray absorption spectroscopy (XAS) for both 1 and 2. EXAFS gave a Ru-Cl distance of 2.416(7) A for 1 and a Ru-OH2O distance of 2.102(6) A for 2. DFT and TDDFT were employed to study the photophysical and photochemical properties of 1. Calculations show that dissociative metal-centered states can be related to the light-induced release of a Cl ligand and subsequent coordination of a solvent molecule. The compound showed no antiproliferative activity in three human carcinoma cell lines (lung, bladder, pancreas) under the testing conditions, either with or without irradiation with UV light.
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Luca Salassa; Tiziana Ruiu; Claudio Garino; Ana M. Pizarro; Fabrizio Bardelli; Diego Gianolio; Aron Westendorf; Patrick J. Bednarski; Carlo Lamberti; Roberto Gobetto; Peter J. Sadler
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2318/82728
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