Spectral properties of polypyridyl ruthenium complexes intercalated in DNA: theoretical insights into the surrounding effects of [Ru(dppz)(bpy)2]2+

Phys Chem Chem Phys. 2012 Sep 28;14(36):12496-504. doi: 10.1039/c2cp40935f. Epub 2012 Jun 14.

Abstract

The UV/Visible absorption properties of a polypyridyl ruthenium complex upon intercalation on DNA are studied at the mixed quantum mechanics molecular mechanics level of theory. Vertical excitation transitions are computed by time dependent density functional theory. Particular emphasis is put on the different levels at which the macromolecular environment is treated, and in particular on the analysis of the effect of mechanical, electrostatic and polarizable embedding. We show that with the highest level of theory the experimental absorption wavelengths are reproduced with a difference of only 2 or 3 nm for the low energy bands. The systematic analysis of the individual vertical transitions allows us to get much more insights into the role played by the environment, in particular, in metal to ligand and intra ligand charge transfer transitions that can lead to the production of DNA oxidative lesions exploitable in phototherapy.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • DNA / chemistry*
  • Models, Molecular
  • Molecular Structure
  • Organometallic Compounds / chemical synthesis
  • Organometallic Compounds / chemistry*
  • Phenazines / chemical synthesis
  • Phenazines / chemistry*
  • Quantum Theory*
  • Spectrophotometry, Ultraviolet

Substances

  • Organometallic Compounds
  • Phenazines
  • bis(2,2'-bipyridyl)(dipyrido(3,2-alpha-2',3'-c)phenazine)ruthenium (II)
  • DNA