“4-N in”卟啉及N-/Neo-Confused卟啉结构和吸收光谱性质的理论研究  

Theoretical studies on the structures and absorption properties of "4-Nin" porphyrins and N-/Neo-confused porphyrins

作　　者：曹洪玉[1,2] 金晓军 张文琼 唐乾[1,2] 王爱玲[3,2] 郑学仿[1,2] CAO Hong-yu;JIN Xiao-jun;ZHANG Weng-qiong;TANG Qian;WANG Ai-ling;ZHENG Xue-fang(College of Life Science and Technology,Dalian University,Dalian116622,China;College of Environmental and Chemical Engineering,Dalian University,Dalian116622,China;Bioorganic Chemistry Key Laboratory,Dalian University,Dalian116622,China)

机构地区：[1]大连大学生命科学与技术学院,辽宁大连116000 [2]大连大学生物有机化学重点实验室,辽宁大连116600 [3]大连大学环境与化学工程学院,辽宁大连116600

出　　处：《化学研究与应用》2018年第8期1277-1285,共9页Chemical Research and Application

基　　金：国家自然科学基金(21571025;21601025;21601024;21601023;21506018)资助;大连市青年科技之星项目支持计划(2017-61)资助

摘　　要："4-N in"卟啉异构体和N-/Neo-Confused卟啉异构体(N-Confused Porphyrin,NCP;Neo-Confused Porphyrin,NECP)是重要的新型光化学材料,因具有特殊的光电特性在各个领域都有广泛的应用。本文利用密度泛函理论(DFT)研究两类卟啉异构体及其金属Zn配合物的几何结构和分子轨道能级。利用GIAO理论所得无配位异构体的核独立化学位移值(NICS)表明这些卟啉异构体具有相近的芳香性质。采用TD-DFT计算了真空和溶剂场极化连续模型下异构体及配合物的吸收光谱,数据表明"4-N in"异构体及其配合物的吸收峰位置都分别较为接近,而与NCP和NECP有较大的差异。金属Zn的配位使NCP和NECP的Q带进一步发生红移,NCP和NECP及其各自的Zn配合物作为光敏材料具有较好的前景。"4-N in"Porphyrin Isomers and N-/Neo-Confused Porphyrin Isomers(N-Confused Porphyrin,NCP;Neo-Confused Porphyrin,NECP)are important new photochemical materials and have been extensively used in various fields due to their special photoelectric properties.The geometry and molecular orbital energy levels of"4-N in"constitutional isomers,N-/Neo-Confused Porphyrin(NCP;NECP)and Zn coordinatedligands were investigated by the density functional theory(DFT)method.Nuclear independent chemical shifts(NICS)of the uncoordinated isomers were estimated with the GIAO theory to illustrate their aromatic.Calculation results showed that these porphyrin isomers exhibit similar aromatic properties.Applied with TD-DFT theory,the absorption spectra of isomers and ligands in the vacuum and solvent field polarization continuous models(IEF-PCM)were obtained.These results demonstrated that"4-N in"isomers have similar spectral characteristics of and ligands,closed absorption peaks in the Soret and Q band,but are quite different from the NCP and NECP.In the Q band,NCP and NECP red-shifted to near 659 nm and 592 nm,respectively,while the oscillator strengths enhanced obviously.The Zn-coordinatedNCP and NECP furtherred shifts to 895 nmand 662 nm in Q band.With the increase of solvent polarities,the Soret bands all red shift,especially NCP and NECP and their respective Zn ligands.The above results provide a theoretical basis for the process of synthesis and utilization of porphyrin isomers in various solvents as potential photo sensing materials.

关 键 词：卟啉异构体 核独立化学位移 密度泛函 含时密度泛函 吸收光谱 

分 类 号：O641.12[理学—物理化学]