单、 双及双混氮杂卟啉的结构和电子吸收光谱

doi:10.7503/cjcu20190413

高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (2): 341.doi: 10.7503/cjcu20190413

单、双及双混氮杂卟啉的结构和电子吸收光谱

曹洪玉^1,^*(),马子辉²,张文琼²,唐乾¹,李如玉²,郑学仿^1,^2,^*()

¹ 大连大学生命科学与技术学院, 大连 116600
² 环境与化学工程学院, 大连 116600

收稿日期:2019-07-24 出版日期:2020-02-10 发布日期:2019-12-10
通讯作者: 曹洪玉,郑学仿 E-mail:caohongyu@foxmail.com;dlxfzheng@126.com
基金资助:
国家自然科学基金(21571025);国家自然科学基金(21601025);国家自然科学基金(21601024);大连市高层次创新人才项目(2017RQ156);大连大学博士启动项目资助

Structures and Electronic Absorption Spectra of N/Neo-Confused, Doubly N-Confused and Neo-Confused N-Confused Porphyrin Isomers ^†

CAO Hongyu^1,^*(),MA Zihui²,ZHANG Wenqiong²,TANG Qian¹,LI Ruyu²,ZHENG Xuefang^1,^2,^*()

¹ College of Life Science and Technology, Dalian 116622, China
² College of Environmental and Chemical Engineering, Dalian University, Dalian 116622, China

Received:2019-07-24 Online:2020-02-10 Published:2019-12-10
Contact: Hongyu CAO,Xuefang ZHENG E-mail:caohongyu@foxmail.com;dlxfzheng@126.com
Supported by:
? Supported by the National Natural Science Foundation of China(21571025);? Supported by the National Natural Science Foundation of China(21601025);? Supported by the National Natural Science Foundation of China(21601024);the Project of Young Science and Technology Star of Dalian, China(2017RQ156);the Special Start-up Fund for Ph.D of Dalian University, China

1. ESM to 341-348.pdf.pdf(2772KB)

摘要/Abstract

摘要：

利用密度泛函和含时密度泛函理论对卟啉(FBP)、单氮杂卟啉(N/Neo-CPs)、双氮杂卟啉(DNCPs)及双混氮杂卟啉(Neo-C-NCPs)的结构与电子吸收光谱进行了研究. 结果表明, 由于N/C位置改变, 分子对称性和轨道组成发生改变, 氮杂卟啉中2-NCP-2H, 2,18-DNCP-2H 和1,17-Neo-C-NCP的各前线和近前线轨道能级发生较大变化, 光谱峰红移较显著; 电子-空穴分布图表明3类氮杂卟啉电子跃迁途径更丰富. 进一步探讨了水、氯仿和苯3种溶剂对4类卟啉分子的影响. 结果表明, 随着溶剂极性减小, FBP, N-/Neo-CPs, DNCPs和Neo-C-NCPs的Q带吸收峰红移越明显, 吸收略有增强.

关键词: 卟啉, 密度泛函理论, 能级轨道, 电子吸收光谱

Abstract:

Three quantum chemistry tools including the density functional theory(DFT), time-dependent density functional theory(TD-DFT) and Multiwfn wave function analysis were utilized to calculate and analyze the geometry, molecular orbital energy levels, absorption spectra and electron-hole distribution of free base porphyrin(FBP), N-/Neo-Confused porphyrins(N/Neo-CPs), doubly N-confused porphyrins(DNCPs) and Neo-confused N-confused porphyrins(Neo-C-NCPs). The calculation results reveal that these isomers display different absorption peaks of the Soret and Q bands due to the carbon-nitrogen-swap structure. The C/N exchange strategy can vary the molecular symmetry and molecular orbital composition of porphyrin derivatives, which results in the molecular orbital energy gaps(HOMO-LUMO) reduction and red shift of absorption peaks. In 2-NCP-2H, 2,18-DNCP-2H and 1,17-Neo-C-NCP, the molecular orbital energy gaps reduce more than others and the characteristic absorption peak red shift. The electron-hole distribution of porphyrins graphically reveals the multiple electron transition pathways in the neotype porphyrin materials. Benzene, chloroform and water were chosen for the further step to explore the effect of environmental polarity on orbital energy levels and electronic absorption spectra. The results illustrate that with the decrease of solvent polarity, the Soret and Q bands of porphyrin derivatives red shift obviously with the oscillator strength slight enhancement.

Key words: Porphyrin, Density functional theory(DFT), Orbital energy level, Electronic absorption spectrum

中图分类号:

O641

TrendMD:

曹洪玉,马子辉,张文琼,唐乾,李如玉,郑学仿. 单、双及双混氮杂卟啉的结构和电子吸收光谱. 高等学校化学学报, 2020, 41(2): 341.

CAO Hongyu,MA Zihui,ZHANG Wenqiong,TANG Qian,LI Ruyu,ZHENG Xuefang. Structures and Electronic Absorption Spectra of N/Neo-Confused, Doubly N-Confused and Neo-Confused N-Confused Porphyrin Isomers ^†. Chem. J. Chinese Universities, 2020, 41(2): 341.

图/表 6

Fig.1 Molecular structures of porphyrin and its isomers

Table 1 Dipole moments(μ) of porphyrin isomers in different polar solvents

Compound	10^-30μ/(C·m)
Compound	Vacuum	Benzene	Chloroform	Water
FBP	0	0	0	0
NECP	4.27	5.50	6.37	7.47
2-NCP-2H	10.88	13.78	15.85	18.58
2-NCP	10.51	12.88	14.51	16.65
2,18-DNCP	28.52	35.86	41.20	48.21
2,18-DNCP-2H	10.44	13.04	14.85	17.15
2,12-DNCP	1.63	1.93	2.07	2.07
1,7-Neo-C-NCP	12.78	15.58	17.48	19.88
1,8-Neo-C-NCP	14.21	17.65	20.12	23.32
1,12-Neo-C-NCP	17.68	22.15	25.32	29.42
1,13-Neo-C-NCP	18.51	23.29	26.65	31.16
1,17-Neo-C-NCP	8.77	10.81	12.28	14.24
1,18-Neo-C-NCP	5.77	6.61	7.07	7.51

Fig.2 Orbital energy levels and the Egap of porphyrin and its isomers a. FBP; b. NECP; c. 2-NCP-2H; d. 2-NCP; e. 2,18-DNCP; f. 2,18-DNCP-2H; g. 2,12-DNCP; h. 1,7-Neo-C-NCP; i. 1,8-Neo-C-NCP; j. 1,12-Neo-C-NCP; k. 1,13-Neo-C-NCP; l. 1,17-Neo-C-NCP; m. 1,18-Neo-C-NCP.

Fig.3 Simulated absorption spectra of porphyrins in vacuum

Fig.4 Hole-electron distributions of S1→S6 states in FBP, 2-NCP-2H, 2,18-DNCP-2H and 1,17-Neo-C-NCP The colors of blue and green indicate hole and electron distribution, respectively.

Fig.5 Simulated absorption spectra of FBP(A), 2-NCP-2H(B) , 2,18-DNCP-2H(C) and 1,17-Neo-C-NCP(D) in vacuum, benzene, chloroform and water

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单、双及双混氮杂卟啉的结构和电子吸收光谱

Structures and Electronic Absorption Spectra of N/Neo-Confused, Doubly N-Confused and Neo-Confused N-Confused Porphyrin Isomers ^†

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单、 双及双混氮杂卟啉的结构和电子吸收光谱

Structures and Electronic Absorption Spectra of N/Neo-Confused, Doubly N-Confused and Neo-Confused N-Confused Porphyrin Isomers †

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单、双及双混氮杂卟啉的结构和电子吸收光谱

Structures and Electronic Absorption Spectra of N/Neo-Confused, Doubly N-Confused and Neo-Confused N-Confused Porphyrin Isomers ^†