N-(2-羟基苯亚甲基)苯胺衍生物分子内质子转移取代基效应的密度泛函理论研究
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摘要
在B3LYP/6-31+G(d,p)水平上研究了N-(2-羟基苯亚甲基)苯胺衍生物分子内质子转移的取代基效应.结果表明:吸电子基引入后会让分子更加趋于平面构型,而供电子基取代后让分子发生了一定程度的扭转;吸电子取代基引入后减小了分子平面的电子密度,拉近了N_1-H_2距离,增强了分子内氢键的强度,降低了醇式到酮式的结构互变能垒.供电子取代基引入后增加了分子平面的电子密度,加大了N_1-H_2间距,减弱了分子内氢键的强度,使得质子转移能垒升高.对分子的前沿轨道研究表明醇式较酮式结构来说更易形成激发态,并且能隙随着吸电子能力和供电子能力增强变小,说明其生物活性变强.
The substituent effect of intramolecular proton transfer of N-(2-hydroxybenzylidene) aniline derivatives were studied at the B3 LYP/6-31 + G(d,p) level.The results show that the introduction of the electron withdrawing group make the molecules more tending to the planar configuration,and the electron donor replace the molecules to a certain degree of torsion.After the introduction of the electron-withdrawing substituents,the electron density of the molecular plane is reduced The N_1-H_2 distance enhances the intramolecular hydrogen bondstrength and reduces the structure of the alcohol to ketone.The electron recombination of the electron donor increases the electron density of the molecular plane,increases the N_1-H_2 spacing,reduces the intensity of the intramolecular hydrogen bonds,and increases the proton transfer energy barrier.The study of the molecular prospective orbit shows that the alcohol is more likely to form an excited state than the ketone structure,and the energy gap decreases with the increase of the electron-withdrawing ability and the electron-supplying ability,which indicates that the biological activity becomes stronger.
The substituent effect of intramolecular proton transfer of N-(2-hydroxybenzylidene) aniline derivatives were studied at the B3 LYP/6-31 + G(d,p) level.The results show that the introduction of the electron withdrawing group make the molecules more tending to the planar configuration,and the electron donor replace the molecules to a certain degree of torsion.After the introduction of the electron-withdrawing substituents,the electron density of the molecular plane is reduced The N_1-H_2 distance enhances the intramolecular hydrogen bondstrength and reduces the structure of the alcohol to ketone.The electron recombination of the electron donor increases the electron density of the molecular plane,increases the N_1-H_2 spacing,reduces the intensity of the intramolecular hydrogen bonds,and increases the proton transfer energy barrier.The study of the molecular prospective orbit shows that the alcohol is more likely to form an excited state than the ketone structure,and the energy gap decreases with the increase of the electron-withdrawing ability and the electron-supplying ability,which indicates that the biological activity becomes stronger.
引文
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[2]Chou P T,Chen Y C,Yu W S,et al.Excited-State intramolecular proton transfer in 10-hydroxybenzo[h]quinoline[J].Journal of Physical Chemistry A,2015,105(10):1731-1740.
[3]Ding K,Courtney S J,Strandjord A J,et al.Excited-state intramolecular proton transfer and vibrational relaxation in 2-(2-hydroxyphenyl)benzothiazole[J].Journal of Physical Chemistry,1983,87(7):18-43.
[4]Sytnik A,Gormin D,Kasha A M.Interplay between excited-state intramolecular proton transfer and charge transfer in flavonols and their use as protein-binding-site fluorescence probes[J].Proceedings of the National Academy of Sciences of the United States of America,1994,91(25):11968-11970.
[5]Nagaoka S I,Nakamura A,Nagashima U.Nodal-plane model for excited-state intramolecular proton transfer of ohydroxybenzaldehyde:substituent effect[J].Journal of Photochemistry and Photobiology A Chemistry,2002,154(1):23-32.
[6]Nagaoka S I,Kusunoki J,Fujibuchi T,et al.Nodal-plane model of the excited-state intramolecular proton transfer of 2-(ohydroxyaryl)benzazoles[J].Journal of Photochemistry and Photobiology A Chemistry,1999,122(3):151-159.
[7]Yi P G,Liang Y H.Theoretical studies of conjugation and substituent effect on intramolecular proton transfer in the ground and excited states[J].Chemical Physics,2006,322(3):382-386.
[8]Alarcón S H,Pagani D,Bacigalupo J,et al.Spectroscopic and semi-empirical MO study of substituent effects on the intramolecular proton transfer in anils of 2-hydroxybenzaldehydes[J].Journal of Molecular Structure,1999,475(2):233-240.
[9]Tran-Thi T H,Prayer C,MilliéP H,et al.Substituent and solvent effects on the nature of the transitions of pyrenol and pyranine.Identification of an intermediate in the excited-state proton-transfer reaction[J].Journal of Physical Chemistry A,2002,106(10):2244-2255.
[10]Klein E,Lukes V.DFT/B3LYP study of the substituent effect on the reaction enthalpies of the individual steps of single electron transfer-proton transfer and sequential proton loss electron transfer mechanisms of phenols antioxidant action[J].Journal of Physical Chemistry A,2006,110(44):12312-12320.
[11]Genin M J,Allwine D A,Anderson D J,et al.Substituent effects on the antibacterial activity of nitrogen-carbon-linked(azolylphenyl)oxazolidinones with expanded activity against the fastidious gram-negative organisms Haemophilus influenzae and Moraxella catarrhalis[J].Journal of Medicinal Chemistry,1999,41(26):5144-5147.
[12]文丽荣,李明,赵桂龙.红外光谱中取代基对苯环骨架振动吸收峰的影响规律[J].光谱实验室,2004,21(2):244-247.
[13]陈新斌,孙咏芬,陈俊琛,等.卟啉化合物荧光性能的取代基效应研究[J].光谱实验室,2006,23(2):374-376.
[14]Chermahini A N,Teimouri A,Beni A S,et al.Theoretical studies on the effect of substituent in the proton transfer reaction of4-substituted pyrazoles[J].Computational&Theoretical Chemistry,2013,1008(4):67-73.
[15]Chai S,Cong S L.Excited state intramolecular proton transfer and substituent effect of 10-hydroxybenzo[h]quinoline:A time-dependent density functional theory study[J].Computational&Theoretical Chemistry,2014,1034(12):80-84.
[16]黎乐民,刘俊婉,金碧辉.密度泛函理论[J].中国基础科学,2007,7(3):27-28.
[17]Lu T,Chen F W.Multiwfn:a multifunctional wavefunction analyzer[J].Journal of Computational Chemistry,2012,33(5):580-592.
[18]Frisch M J,Trucks G W,Schlegel H B,et al.Gaussian 09 revision C.01[M].Wallingford:Gaussian Inc,CT,2009.
[19]易平贵,彭洪亮,于贤勇,等.2-(2-巯苯基)苯并噁唑分子内质子转移取代基电子效应的密度泛函理论研究[J].化学学报,2010,68(9):875-882.
[20]Sudha S,Karabacak M,Kurt M,et al.Molecular structure,vibrational spectroscopic,first-order hyperpolarizability and HOMO,LUMO studies of 2-aminobenzimidazole[J].Spectrochimica Acta Part A Molecular&Biomolecular Spectroscopy,2011,84(1):184-195.
[21]Arivazhagan M,Jeyavijayan S.Vibrational spectroscopic,first-order hyperpolarizability and HOMO,LUMO studies of 4-chloro-2-(trifluoromethyl)aniline based on DFT calculations[J].Spectrochimica Acta Part A Molecular&Biomolecular Spectroscopy,2011,79(2):376-383.