Study of the Photophysical Properties and the DNA Binding of Enantiopure [Cr(TMP)(dppn)] Complex

Overview

Journal Inorg Chem

Specialty Chemistry

Date 2024 Dec 3

PMID 39626123

Authors

Daniel Graczyk

Rory A Cowin

Dimitri Chekulaev

Maisie A Haigh

Paul A Scattergood

Susan J Quinn

Affiliations

Soon will be listed here.

Abstract

The preparation, electrochemistry and photophysical properties of a heteroleptic chromium(III) polypyridyl complex [Cr(TMP)(dppn)] () containing two 3,4,7,8-tetramethyl-1,10-phenanthroline (TMP) ligands and the π-extended benzodipyrido[3,2-a:2',3'-]phenazine (dppn) ligand are reported. The visible absorption spectrum of reveals distinct bands between 320 and 420 nm characteristic of dppn-based ligand-centered transitions, with found to be nonemissive in aqueous solution but weakly luminescent in aerated acetonitrile solution. Transient visible absorption (TrA) spectroscopy reveals that 400 nm excitation of leads to initial population of a ligand-to-metal charge transfer (LMCT) state which evolves within tens of ps to form a dppn-localized intraligand (IL) state which persists for longer than 7 ns and efficiently sensitizes singlet oxygen. Chiral resolution and DNA binding of the lambda and delta enantiomers of to four different DNA systems is reported. In all cases the lambda enantiomer shows greater affinity for DNA and in particular AT-rich DNA. Thermal denaturation reveals that the lambda enantiomer stabilizes the DNA more. There is also a greater stabilization of the AT-containing DNA sequences compared to GC DNA.

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