Photochemistry and DNA photocleavage by a new unsupported dirhodium(II,II) complex. Academic Article

abstract

• The new complex [Rh2(phen)2(CH3CN)6](BF4)4 (1) was synthesized and characterized in solution and its crystal structure was determined. Irradiation of 1 with visible light (irr>590nm) in water results in the release of two equatorial CH3CN ligands, CH3CNeq, as well as in the formation of mononuclear radical Rh(II) fragments stemming from the homolytic photocleavage of the metal-metal bond. The photoproducts, identified by electrospray ionization mass spectrometry, include [Rh(phen)(CH3CN)(OH)](+) and [Rh(phen)(CH3CN)(H2O)3(BF4)](+). The quantum yield for the photochemical transformation of 1 in H2O exceeds unity (550nm=1.38) indicative of dark reactions following the initial photoprocess. DNA photocleavage was observed for 1 (irr>590nm), whereas the complex is unreactive in the dark. This feature makes 1 a promising photodynamic therapy agent that does not operate via the production of singlet oxygen, 1O2.

authors

• Dunbar, Kim

published proceedings

• Philos Trans A Math Phys Eng Sci

author list (cited authors)

• Li, Z., Burya, S. J., Turro, C., & Dunbar, K. R.

citation count

• 11

complete list of authors

• Li, Zhanyong||Burya, Scott J||Turro, Claudia||Dunbar, Kim R

publication date

• July 2013

publisher

• The Royal Society  Publisher

published in

• Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences  Journal

keywords

• Binding Sites
• DNA
• Glutathione
• Ligand Exchange
• Light
• Photochemistry
• Photochemotherapy
• Photodynamic Therapy
• Radiation Dosage
• Rhodium

PubMed Central ID

• 23776291

Digital Object Identifier (DOI)

• 10.1098/rsta.2012.0128

start page

• 20120128

end page

• 20120128

volume

• 371

issue

• 1995

URL

• http://dx.doi.org/10.1098/rsta.2012.0128