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Issue 8, 2015
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Photoinduced interactions of two dirhodium complexes with d(GTCGAC)2 probed by 2D NOESY

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Abstract

The interactions between the 6-mer duplex oligonucleotide d(GTCGAC)2 and the photoactive dirhodium complexes cis-H,H-[Rh2(HNOCCH3)2(L)(CH3CN)4]2+, where L represents bpy (1, 2,2′-bipyridine) and dppz (2, dipyrido[3,2-a:2′,3′-c]phenazine), were probed using 2D 1H–1H NOESY NMR spectroscopy. Complex 1 does not interact with the duplex in the dark, but binds covalently to the terminal guanine following irradiation with visible light. Similar behavior was observed for 2, but in addition to the photoinduced covalent DNA binding, the planar dppz ligand of the complex shields the terminal cytosine protons after irradiation. The results are consistent with photoinduced guanine coordination and end-capping of the duplex through π-stacking interactions with the terminal GC base pair. These data show that in the presence of the 6-mer duplex oligonucleotide, 1 and 2 exhibit photoinduced covalent binding to DNA. In addition, the π-stacking interactions of 2 with the duplex are enhanced upon irradiation.

Graphical abstract: Photoinduced interactions of two dirhodium complexes with d(GTCGAC)2 probed by 2D NOESY

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Supplementary files

Article information


Submitted
09 Oct 2014
Accepted
16 Dec 2014
First published
05 Jan 2015

Dalton Trans., 2015,44, 3640-3646
Article type
Paper
Author version available

Photoinduced interactions of two dirhodium complexes with d(GTCGAC)2 probed by 2D NOESY

A. M. Palmer, J. D. Knoll and C. Turro, Dalton Trans., 2015, 44, 3640
DOI: 10.1039/C4DT03119A

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