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The Royal Society, Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 1995(371), p. 20120128, 2013

DOI: 10.1098/rsta.2012.0128

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

Journal article published in 2013 by Zhanyong Li ORCID, Scott J. Burya, Claudia Turro, Kim R. Dunbar
This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Abstract

The new complex [Rh 2 (phen) 2 (CH 3 CN) 6 ](BF 4 ) 4 ( 1 ) was synthesized and characterized in solution and its crystal structure was determined. Irradiation of 1 with visible light ( λ irr >590 nm) in water results in the release of two equatorial CH 3 CN ligands, CH 3 CN eq , 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)(CH 3 CN)(OH)] + and [Rh(phen)(CH 3 CN)(H 2 O) 3 (BF 4 )] + . The quantum yield for the photochemical transformation of 1 in H 2 O exceeds unity ( Φ 550 nm =1.38) indicative of dark reactions following the initial photoprocess. DNA photocleavage was observed for 1 ( λ irr >590 nm), 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, 1 O 2 .