| 锰(III)5,10,15-三(五氟苯基)-Corrole配合物的DFT计算 |
| |
| 引用本文： | 刘海洋,李立,应晓,王湘利,徐志广,廖世军,张启光.锰(III)5,10,15-三(五氟苯基)-Corrole配合物的DFT计算[J].物理化学学报,2008,24(9):1602-1608. |
| |
| 作者姓名： | 刘海洋 李立 应晓 王湘利 徐志广 廖世军 张启光 |
| |
| 作者单位： | Department of Chemistry, South China University of Technology, Guangzhou 510641, P. R. China; Department of Chemistry, The Hong Kong University of Science and Technology, Hong Kong, P. R. China; Department of Applied Physics, South China University of Technology, Guangzhou 510641, P. R. China; School of Chemistry and Environment, South China Normal University, Guangzhou 510631, P. R. China |
| |
| 摘 要： | 在6-31G*水平上采用DFT(UB3LYP)方法对锰(III)5,10,15-三(五氟苯基)-corrole (TPFC)MnIII]及其咪唑轴向配位加合物(TPFC)MnIII(Im)进行了几何结构全优化. 计算结果表明, 咪唑的配位作用不会改变其基态的高自旋(s=2)特性. (TPFC)MnIII与咪唑配位形成轴向加合物后, 其中心金属Mn原子偏离平面结构, 与corrole大环N4平均平面的距离达到0.02734 nm. NBO分析显示(TPFC)MnIII和(TPFC)MnIII(Im)中心金属锰的电子组态为(dxz)1(dyz)1(dz2)1(dx2-y2)1(dxy)0. (TPFC)MnIII(Im)前线分子轨道能级明显上升, 从其β-(LUMO+3)轨道可见咪唑配位N原子的py轨道与中心金属Mn原子dyz轨道形成了d-pπ轨道. TD-DFT计算发现, (TPFC)MnIII和(TPFC)MnIII(Im)电子光谱Q带的“四轨”特征比B 带明显; (TPFC)MnIII的CT带主要源自β-(HOMO-1)→β-(LUMO+5)和β-HOMO→β-(LUMO+4)的跃迁, (TPFC)MnIII(Im)的CT带则主要源自β-(HOMO-1)→β-(LUMO+3)和β-HOMO→β-(LUMO+4)的跃迁.
|
| 关 键 词： | 锰(III) corrole 轴向配体 咪唑 DFT 电子光谱 |
| 收稿时间： | 2008-03-10 |
| 修稿时间： | 2008-04-09 |
DFT Calculations on Manganese(III)5,10,15-Tris(pentafluorophenyl)-Corrole |
| |
| LIU Hai-Yang,LI Li,YING Xiao,WANG Xiang-Li,XU Zhi-Guang,LIAO Shi-Jun,CHANG Chi-Kwong.DFT Calculations on Manganese(III)5,10,15-Tris(pentafluorophenyl)-Corrole[J].Acta Physico-Chimica Sinica,2008,24(9):1602-1608. |
| |
| Authors: | LIU Hai-Yang LI Li YING Xiao WANG Xiang-Li XU Zhi-Guang LIAO Shi-Jun CHANG Chi-Kwong |
| |
| Institution: | Department of Chemistry, South China University of Technology, Guangzhou 510641, P. R. China; Department of Chemistry, The Hong Kong University of Science and Technology, Hong Kong, P. R. China; Department of Applied Physics, South China University of Technology, Guangzhou 510641, P. R. China; School of Chemistry and Environment, South China Normal University, Guangzhou 510631, P. R. China |
| |
| Abstract: | Geometries of manganese (III) 5,10,15-tris(pentafluorophenyl) corrole (TPFC)MnIII and its imidazole axial binding adduct (TPFC)MnIII(Im) were optimized by using DFT(UB3LYP) method at 6-31G* basis set level. Calculation results indicated that (TPFC)MnIII and (TPFC)MnIII(Im) had the same spin state (s=2) in their ground states. (TPFC) MnIII had a plane structure, whileMn atomin (TPFC)MnIII(Im) was above the corrole N4mean plane 0.02734 nm. NBOanalysis showed that the electronic configuration of centralMn atomin (TPFC)MnIII and (TPFC)MnIII(Im) was (dxz)1(dyz)1(dz2 )1(dx2-y2)1(dxy)0. The energies of frontier orbitals of (TPFC)MnIII(Im) were significantly higher than those of (TPFC)MnIII, and the Mn-imidazole d-pπ bonding could be found from β-(LUMO+3) obital of (TPFC)MnIII(Im). In addition, electronic spectra of (TPFC)MnIII and (TPFC)MnIII(Im) were calculated by using TD-UB3LYP/6-31G* method, and it could be found that Q band had more“four-orbital”characters than B band. CT band of (TPFC)MnIII was mainly contributed from β-(HOMO-1) to β-(LUMO+5) and β-HOMO to β-(LUMO+4) transitions, and CT band of (TPFC)MnIII(Im) was mainly contributed from β-(HOMO-1) to β-(LUMO+3) and β-HOMO to β-(LUMO+4) transitions. |
| |
| Keywords: | Manganese (III) corrole Axial ligand Imidazole DFT Electronic spectrum |
|
| 点击此处可从《物理化学学报》浏览原始摘要信息 |
| 点击此处可从《物理化学学报》下载免费的PDF全文 |
|
