Nucleobase Stacking Sustained by Pt−Pt Interactions

• Published in: ChemistryEurope 2024-03, Vol.2 (2), p.n/a
• Main Authors: Lorenzo‐Aparicio, Carmen, García‐Álvarez, Pablo, Cabeza, Javier A., Gómez‐Gallego, Mar, Sierra, Miguel A.
• Format: Article
• Language: English
• Subjects: Binuclear complexes; Chiral helixes; Chromatography; Ligands; Nucleobase stacking; Pt−Pt interactions; Spectrum analysis
• ISSN: 2751-4765; 2751-4765
• DOI: 10.1002/ceur.202300065

This article reports the use of metal–metal interactions as a way to induce nucleobase stacking in a dinucleotide chain. We synthetized and study a series of C,N‐cyclometallated platinum(II) binuclear complexes derived from 6‐phenylpurine dinucleotide 1 as proligand, and β‐diketonates, 2,2'‐bipyridines and 1,10‐phenanthroline as ancillary ligands. The X‐ray diffraction analysis revealed that the diketonate derivatives 7 and 8 are chiral helixes sustained by Pt−Pt intramolecular interactions that allow the nucleobase stacking. The folded helical structures are maintained in solution, as demonstrated by the appearance of metal–metal‐to‐ligand charge‐transfer (MMLCT) transitions in the UV‐vis spectra. The influence of the ancillary ligand in the molecular structure was evidenced by the absence of bands derived from M−M interactions in the absorption spectra of 2,2’‐bipyridine and and 1,10‐phenanthroline derivatives 12–14. The existence of Pt−Pt in the complexes of this study can be also detected by electrochemistry. Pt⋅⋅⋅Pt interactions are able to provoke the folding of a dinucleotide chain favoring intramolecular nucleobase stacking. This proof of concept shows the potential of M−M interactions to promote the folding and subsequent nucleobase stacking in an oligonucleotide chain.