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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Density functional theory/time-dependent DFT studies on the structures, trend in DNA-binding affinities, and spectral properties of complexes [Ru(bpy)(2)(p-R-pip)](2+) (R = -OH, -CH3, -H, -NO2)
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Density functional theory/time-dependent DFT studies on the structures, trend in DNA-binding affinities, and spectral properties of complexes [Ru(bpy)(2)(p-R-pip)](2+) (R = -OH, -CH3, -H, -NO2)

机译：[Ru（bpy）（2）（pR-pip）]（2+）的密度泛函理论/时间依赖性DFT研究结构，DNA结合亲和力和光谱性质（R = -OH，- CH3，-H，-NO2）

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Studies on the electronic structures and trend in DNA-binding affinities of a series of Ru(II) complexes [Ru(bpy)(2)(p-R-pip)](2+) (bpy = 2,2-bipyridine; pip = 2-phenylimidazo[4,5- f] [1,10]-phenanthroline; R = -OH, -CH3, -H, -NO2) 1-4 have been carried out, using the density functional theory (DFT) at the B3LYP/ LanL2DZ level. The electronic absorption spectra of these complexes were also investigated using time-dependent DFT (TDDFT) at the B3LYP//LanL2DZ/6- 31G level. The computational results show that the substituents on the parent ligand ( pip) have a significant effect on the electronic structures of the complexes, in particular, on the energies of the lowest unoccupied molecular orbital (LUMO) and near some unoccupied molecular orbitals (LUMO + x, x = 1-4). With the increase in electron-withdrawing ability of the substituent in this series, the LUMO + x (x = 0-4) energies of the complexes are substantially reduced in order, for example, epsilon(LUMO)(1) approximate to epsilon(LUMO)(2) > epsilon(LUMO)(3) > epsilon(LUMO)(4), whereas the pi-component populations of the LUMO+x (x = 0-4) are not substantially different. Combining the consideration of the bigger steric hindrance of complex 2, the trend in DNA-binding affinities (K-b) of the complexes, that is, K-b(2) < K-b(1) < K-b(3) < K-b(4) can be reasonably explained. In addition, the experimental singlet metal-to-ligand charge transfer ((MLCT)-M-1) spectra of these complexes can be well simulated and discussed by the TDDFT calculations.
机译：一系列Ru（II）配合物[Ru（bpy）（2）（pR-pip）]（2+）（bpy = 2,2-bipyridine; pip =使用密度泛函理论（DFT）在2-苯基咪唑并[4,5-f] [1,10]-菲咯啉; R = -OH，-CH3，-H，-NO2）1-4处进行了研究。 B3LYP / LanL2DZ级别。还使用时间依赖性DFT（TDDFT）在B3LYP // LanL2DZ / 6-31G浓度下研究了这些络合物的电子吸收光谱。计算结果表明，母体配体（pip）上的取代基对配合物的电子结构具有重要影响，特别是对最低未占据分子轨道（LUMO）和接近一些未占据分子轨道（LUMO + x，x = 1-4）。随着该系列取代基吸电子能力的提高，配合物的LUMO + x（x = 0-4）能量大幅度降低，例如，ε（LUMO）（1）近似于ε（ LUMO）（2）> epsilon（LUMO）（3）> epsilon（LUMO）（4），而LUMO + x（x = 0-4）的pi组分数量基本没有差异。结合对复合物2的更大位阻的考虑，复合物的DNA结合亲和力（Kb）趋势即Kb（2）

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