Theoretical studies on DNA-photocleavage efficiencies and mechanisms of Ru(II) polypyridyl complexes.
Theoretical studies on the DNA-photocleavage efficiencies and mechanisms of Ru(II) complexes [Ru(bpy)(2)(L)](2+) (bpy = 2,2'-bipyridine; L: dppz = dipyrido[3,2-a:2',3'-c]phenazine; mitatp = 5-methoxy-isatino[1,2-b]-1,4,8,9-tetraazatriphenylene; nitatp = 5-nitro-isatino [1,2-b]-1,4,8,9-tetraazatriphenylene) 1-3 were carried out using density functional theory (DFT). First, the accuracies of redox potentials computed for [Ru(bpy)(3)](2+) in the ground state and the excited state by different computational methods were tested, and then the redox potentials of complexes 1-3 in their excited states were computed accurately. Secondly, the trend in the DNA-photocleavage efficiencies (ϕ) of complexes 1-3 [i.e., ϕ(2) > ϕ(3) > ϕ(1)] was reasonably well explained by their excited-state reduction potentials and their electron-transfer activation energies. Finally, the photoinduced oxidation-reduction mechanism utilized by these complexes was explored, and the DNA-photocleavage process was explained rationally.
College of Chemistry and Materials Science, Huaibei Normal University, Huaibei, 235000, China. miaotifang@163.com
Ti-Fang
TF
Miao
Shuang
S
Li
Jin-Can
JC
Chen
Fang
F
Ma
Kang-Cheng
KC
Zheng
D015082:2,2'-Dipyridyl / Q000737:chemistry*; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D004247:DNA / Q000737:chemistry* / Q000528:radiation effects; D008027:Light; D008962:Models, Theoretical; D011789:Quantum Theory; D012428:Ruthenium / Q000737:chemistry*
D056831:Coordination Complexes; D015082:2,2'-Dipyridyl; D012428:Ruthenium; D004247:DNA