Spectral properties of polypyridyl ruthenium complexes intercalated in DNA: theoretical insights into the surrounding effects of [Ru(dppz)(bpy)2]2+.
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.
Equipe de Chimie et Biochimie Théoriques SRSMC, Université de Lorraine Nancy, BP 70239, Boulevard des Aiguillettes, 54506 Vandoeuvre-lés-Nancy, France.
Thibaut
T
Very
Stéphane
S
Despax
Pascal
P
Hébraud
Antonio
A
Monari
Xavier
X
Assfeld
D004247:DNA / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010619:Phenazines / Q000138:chemical synthesis / Q000737:chemistry*; D011789:Quantum Theory; D013056:Spectrophotometry, Ultraviolet
D009942:Organometallic Compounds; D010619:Phenazines; C077849:bis(2,2'-bipyridyl)(dipyrido(3,2-alpha-2',3'-c)phenazine)ruthenium (II); D004247:DNA