基本信息来源于合作网站,原文需代理用户跳转至来源网站获取       
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.
推荐文章
A re-assessment of nickel-doping method in iron isotope analysis on rock samples using multi-collect
Fe isotope
Ni-doping
Stable isotope
Precision and accuracy
Mass bias correction
Pseudo-high mass resolution
LFMO和NBO的定域性和作用能解析
自然键轨道
定域片断分子轨道
一次性对角化
Morokuma能量分解
垂直共振能
NbO电解电容器的结构及制造工艺新进展
NbO电解电容器
低价铌氧化物
综述
结构
制造工艺
内容分析
关键词云
关键词热度
相关文献总数  
(/次)
(/年)
文献信息
篇名 NBO Population Analysis and Electronic Calculation of Four Azopyridine Ruthenium Complexes by DFT Method
来源期刊 计算化学(英文) 学科 化学
关键词 Natural BOND ORBITAL (NBO) HOMO LUMO Azopyridine Ligand MLCT LLCT
年,卷(期) 2017,(1) 所属期刊栏目
研究方向 页码范围 51-64
页数 14页 分类号 O6
字数 语种
DOI
五维指标
传播情况
(/次)
(/年)
引文网络
引文网络
二级参考文献  (0)
共引文献  (0)
参考文献  (0)
节点文献
引证文献  (0)
同被引文献  (0)
二级引证文献  (0)
2017(0)
  • 参考文献(0)
  • 二级参考文献(0)
  • 引证文献(0)
  • 二级引证文献(0)
研究主题发展历程
节点文献
Natural
BOND
ORBITAL
(NBO)
HOMO
LUMO
Azopyridine
Ligand
MLCT
LLCT
研究起点
研究来源
研究分支
研究去脉
引文网络交叉学科
相关学者/机构
期刊影响力
计算化学(英文)
季刊
2332-5968
武汉市江夏区汤逊湖北路38号光谷总部空间
出版文献量(篇)
53
总下载数(次)
0
总被引数(次)
0
论文1v1指导