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NBO Population Analysis and Electronic Calculation of Four Azopyridine Ruthenium Complexes by DFT Method

机译：DFT法分析四种氮杂吡啶钌配合物的NBO种群和电子计算

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摘要

The molecular structure, the Natural Bond orbital (NBO) and the Time Dependent-DFT of both isomers cis or γ-Cl and trans or δ-Cl of RuCl2(L)2, where L stands respectively for 2-phenylazopyridine (Azpy), 2,4-dimethyl-6-[phenylazo]pyridine (Dazpy), 2-[(3,5-dimethylphenyl)azopyridine] (Mazpy) and 2-pyridylazonaphtol (Nazpy) were calculated with DFT method at B3LYP/LANL2DZ level. The prediction of the frontier orbitals (Highest Occupied Molecular Orbital or HOMO and Lowest Unoccupied Molecular Orbital or LUMO) shows that the most active complexes suitable for electronic reactions are admitted to be the trans isomers. Moreover, δ-RuCl2 (Azpy)2 is discovered to react more actively as photo-sensitizer since its energy gap is the minimum. Besides, electronic structures of all complexes through NBO calculation indicate that Ru-N bonds are made of delocalization of occupancies from lone pair orbital of N atoms to the ruthenium. Moreover, Ru was assumed to have almost the same charge regardless the structure of the azopyridine ligands in the complex indicating that the ligands provide only a steric effect that is responsible for the ruthenium’s selectivity. Concerning the transition state, NBO analysis also highlights that the transition LP(Ru) π*(N1-N2) does correspond to t2g?π*(L). This transition is assumed to correspond to Metal to Ligand Charge Transfer (MLCT) that is responsible for the photo-sensitiveness of the metallic complex. Besides, TDDFT calculation of complexes showed that δ-RuCl2(Nazpy)2 displays the largest band during the absorption. For that reason, it is admitted to be the best photosensitizer due to a large system of conjugation provided by Nazpy ligand.
机译：RuCl2（L）2的两个异构体顺式或γ-Cl和反式或δ-Cl的分子结构，天然键轨道（NBO）和随时间变化的DFT，其中L分别表示2-苯基偶氮吡啶（Azpy），通过DFT法在B3LYP / LANL2DZ水平上计算2，4-二甲基-6- [苯基偶氮]吡啶（Dazpy），2-[（（3,5-二甲基苯基）偶氮吡啶]（Mazpy）和2-吡啶基ona唑烷（Nazpy）。前沿轨道（最高占据分子轨道或HOMO和最低未占据分子轨道或LUMO）的预测表明，适用于电子反应的活性最高的络合物是反式异构体。此外，发现δ-RuCl2（Azpy）2作为光敏剂能更积极地反应，因为它的能隙最小。此外，通过NBO计算得出的所有配合物的电子结构表明，Ru-N键是由占据空间从N原子的孤对轨道到钌的离域化构成的。此外，无论复合物中的偶氮吡啶配体的结构如何，Ru都被认为具有几乎相同的电荷，这表明该配体仅提供位阻效应，从而影响了钌的选择性。关于过渡状态，NBO分析还强调过渡LP（Ru）π*（N1-N2）确实对应于t2g？π*（L）。假定该过渡对应于负责金属络合物光敏性的金属到配体的电荷转移（MLCT）。此外，配合物的TDDFT计算表明，δ-RuCl2（Nazpy）2在吸收过程中显示出最大的谱带。因此，由于Nazpy配体提供的大量共轭体系，它被认为是最好的光敏剂。

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