Photodissociation of a ruthenium(II) arene complex and its subsequent interactions with biomolecules: a density functional theory study.
The piano-stool Ru(II) arene complex [(η⁶-benz)Ru(bpm)(py)]²⁺ (benz = benzene, bpm = 2,2'-bipyrimidine, and py = pyridine), which is conventionally nonlabile (on a timescale and under conditions relevant for biological reactivity), can be activated by visible light to selectively photodissociate the monodentate ligand (py). In the present study, the aquation and binding of the photocontrolled ruthenium(II) arene complex [(η⁶-benz)Ru(bpm)(py)]²⁺ to various biomolecules are studied by density functional theory (DFT) and time-dependent DFT (TDDFT). Potential energy curves (PECs) calculated for the Ru-N (py) bonds in [(η⁶-benz)Ru(bpm)(py)]²⁺ in the singlet and triplet state give useful insights into the photodissociation mechanism of py. The binding energies of the various biomolecules are calculated, which allows the order of binding affinities among the considered nuleic-acid- or protein-binding sites to be discerned. The kinetics for the replacement of water in the aqua complex with biomolecules is also considered, and the results demonstrate that guanine is superior to other biomolecules in terms of coordinating with the Ru(II) aqua adduct, which is in reasonable agreement with experimental observations.
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry/KLGHEI of Environment and Energy Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, People's Republic of China.
Hanlu
H
Wang
Nathan J
NJ
DeYonker
Xiting
X
Zhang
Cunyuan
C
Zhao
Liangnian
L
Ji
Zong-Wan
ZW
Mao
D004247:DNA / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D055668:Photochemical Processes; D011506:Proteins / Q000737:chemistry*; D011789:Quantum Theory; D012428:Ruthenium / Q000737:chemistry*; D012996:Solutions; D013056:Spectrophotometry, Ultraviolet; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
D009942:Organometallic Compounds; D011506:Proteins; D012996:Solutions; D014867:Water; D012428:Ruthenium; D004247:DNA