EXAFS, DFT, Light-Induced Nucleobase Binding, and Cytotoxicity of the Photoactive Complex cis-[Ru(bpy)2(CO)Cl]+
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- 作者：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
- 刊名：Organometallics
- 出版年：2010
- 出版时间：December 27, 2010
- 年：2010
- 卷：29
- 期：24
- 页码：6703-6710
- 全文大小：907K
- 年卷期：v.29,no.24(December 27, 2010)
- ISSN：1520-6041
文摘
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) Å for 1 and a Ru−OH2O distance of 2.102(6) Å 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.