Substituted group and side chain effects for the porphyrin and zinc(II)–porphyrin derivatives: A DFT and TD-DFT study

doi:10.1016/j.jlumin.2013.03.037

機構典藏 > College of Sciences > Graduate Institute & Department of Chemistry > Journal Article > Item 987654321/98701

Please use this identifier to cite or link to this item: https://tkuir.lib.tku.edu.tw/dspace/handle/987654321/98701

Title:	Substituted group and side chain effects for the porphyrin and zinc(II)–porphyrin derivatives: A DFT and TD-DFT study
Authors:	Tai, Chin-Kuen;Chuang, Wen-Hua;Wang, Bo-Cheng
Contributors:	淡江大學化學學系
Keywords:	Porphyrin and zinc(II)–porphyrin;Substitution effect;Side chain effect;DFT
Date:	2013-10
Issue Date:	2014-09-15 14:24:45 (UTC+8)
Publisher:	Amsterdam: Elsevier BV * North-Holland
Abstract:	The DFT/B3LYP/LANL2DZ and TD-DFT calculations have been performed to generate the optimized structures, electronic and photo-physical properties for the porphyrin and zinc(II)–porphyrin (metalloporphyrin) derivatives. The substituted group and side chain effects for these derivatives are discussed in this study. According to the calculation results, the side chain moiety extends the π-delocalization length from the porphyrin core to the side chain moiety. The substituted group with a stronger electron-donating ability increases the energy level of highest occupied molecular orbital (EHOMO). The side chain moiety with a lower resonance energy decreases EHOMO, the energy level of the lowest unoccupied molecular orbital (ELUMO), and the energy gap (Eg) between HOMO and LUMO in the porphyrin and zinc(II)–porphyrin derivatives. The natural bonding orbital (NBO) analysis determines the possible electron transfer mechanism from the electron-donating to -withdrawing groups (the side chain moiety) in these porphyrin derivatives. The projected density of state (PDOS) analysis shows that the electron-donating group affects the electron density distribution in both HOMO and LUMO, and the side chain moiety influence the electron density distribution in LUMO. The calculated photo-physical properties (absorption wavelengths and the related oscillator strength, f) in dichloromethane environment for porphyrin and zinc(II)–porphyrin derivatives have been simulated by using the TD-DFT method within the Polarizable Continuum Model (PCM). The present of both of the substituted group and the side chain moiety in these derivatives results in a red shift and broadening of the range of the absorption peaks of the Q/Soret band as compared to porphin.
Relation:	Journal of Luminescence 142, pp.8–16
DOI:	10.1016/j.jlumin.2013.03.037
Appears in Collections:	[Graduate Institute & Department of Chemistry] Journal Article

Files in This Item:

File	Description	Size	Format
index.html		0Kb	HTML	263	View/Open

Loading...