物理化学学报 >> 2008, Vol. 24 >> Issue (09): 1602-1608.doi: 10.3866/PKU.WHXB20080913

研究论文 上一篇    下一篇

锰(III)5,10,15-三(五氟苯基)-Corrole配合物的DFT计算

刘海洋; 李立; 应晓; 王湘利; 徐志广; 廖世军; 张启光   

  1. 华南理工大学化学系, 广州 510641; 香港科技大学化学系, 香港; 华南理工大学应用物理系, 广州 510641; 华南师范大学化学与环境学院, 广州10631
  • 收稿日期:2008-03-10 修回日期:2008-04-09 发布日期:2008-09-10
  • 通讯作者: 刘海洋; 张启光 E-mail:chhyliu@scut.edu.cn;chang@ust.hk

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   

  1. 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
  • Received:2008-03-10 Revised:2008-04-09 Published:2008-09-10
  • Contact: LIU Hai-Yang; CHANG Chi-Kwong E-mail:chhyliu@scut.edu.cn;chang@ust.hk

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

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.

Key words: Manganese (III) corrole, Axial ligand, Imidazole, DFT, Electronic spectrum

MSC2000: 

  • O641