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

doi:10.7503/cjcu20190413

Abstract

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

CLC Number:

O641

TrendMD:

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 ^†[J]. Chem. J. Chinese Universities, 2020, 41(2): 341.

Figures/Tables 6

Fig.1 Molecular structures of porphyrin and its isomers

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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