2-氨基-3-苯并恶唑喹啉水复合物激发态分子内与分子间质子转移的竞争机理
|
摘要
基于密度泛函与含时密度泛函理论方法,研究2-氨基-3-苯并恶唑喹啉(ABO)水复合物(ABO-H_2O)激发态分子内与分子间质子转移的竞争机理.结果表明:ABO-H_2O复合物中存在一个分子内的氢键和两个分子间的氢键;基态ABO-H_2O复合物被激发至第一电子激发态后,仅需越过一个34.157kJ/mol能垒,复合物即可发生激发态分子内的质子转移反应;ABO-H_2O复合物激发态分子间的双质子转移过程中存在一个63.585kJ/mol能垒;在第一电子激发态上,ABO-H_2O复合物中存在分子内与分子间质子转移的竞争机制;ABO-H_2O复合物更易出现激发态分子内的质子转移过程.
We investigated the competition mechanism of intramolecular and intermolecular proton transfer of 2-amino-3-(2′-benzoxazolyl)-quinoline-H_2O(ABO-H_2O)water complex in the excited states by means of the density functional theory and time-dependent density functional theory.The results show that there is an intramolecular hydrogen bond and two intermolecular hydrogen bonds in the ABO-H_2O complex.When the complex in the ground state is excited to the first electron excited state,only a 34.157 kJ/mol energy barrier is needed for the ABO-H_2O complex to occur intramolecular proton transfer reaction.There is a 63.585 kJ/mol energy barrier in the intermolecular double proton transfer process of the ABO-H_2O complex in the excited state.There is a competitive mechanism for intramolecular and intermolecular proton transfer processes of the ABO-H_2O complex in the first electron excited state.The excited state intramolecular proton transfer process is more likely to take place for the ABO-H_2O complex.
We investigated the competition mechanism of intramolecular and intermolecular proton transfer of 2-amino-3-(2′-benzoxazolyl)-quinoline-H_2O(ABO-H_2O)water complex in the excited states by means of the density functional theory and time-dependent density functional theory.The results show that there is an intramolecular hydrogen bond and two intermolecular hydrogen bonds in the ABO-H_2O complex.When the complex in the ground state is excited to the first electron excited state,only a 34.157 kJ/mol energy barrier is needed for the ABO-H_2O complex to occur intramolecular proton transfer reaction.There is a 63.585 kJ/mol energy barrier in the intermolecular double proton transfer process of the ABO-H_2O complex in the excited state.There is a competitive mechanism for intramolecular and intermolecular proton transfer processes of the ABO-H_2O complex in the first electron excited state.The excited state intramolecular proton transfer process is more likely to take place for the ABO-H_2O complex.
引文
[1]KHIMICH M N,IVANOV V L,MELNIKOV M Y,et al.Dynamics of Excited-State Intramolecular ProtonTransfer in 2-Amino-3-(2′-benzazolyl)quinoline Cations[J].Photochemical&Photobiological Sciences,2017,16(7):1139-1145.
[2]余江虹,原鲜霞,贾超,等.氨基喹啉及其衍生物的性质、合成和应用[J].化学世界,2009(2):122-126.(YU Jianghong,YUAN Xianxia,JIA Chao,et al.Property,Synthesis and Application of Aminoquinoline Series[J].Chemistry World,2009(2):122-126.)
[3]JIA Xueli,LI Chaozheng,LI Donglin,et al.TDDFT Study on Excited State Intramolecular Proton Transfer Mechanism in 2-Amino-3-(2′-benzazolyl)-quinolines[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2018,192:168-173.
[4]KHIMICH M N,IVANOV V L,MEL’NIKOV M Y,et al.Peculiarities of Exited State Intramolecular Proton Transfer in 2-Amino-3-(2′-benzazolyl)-quinolines[J].High Energy Chemistry,2017,51(1):17-23.
[5]WANG Ye,YIN Hang,SHI Ying,et al.Ground-State and Excited-State Multiple Proton Transfer via a Hydrogen-Bonded Water Wire for 3-Hydroxypyridine[J].New Journal of Chemistry,2014,38(9):4458-4464.
[6]辛春雨,王野.7-羟基黄酮分子在水中分子内电荷转移及分子间多重质子的转移机制[J].吉林大学学报(理学版),2017,55(5):1317-1322.(XIN Chunyu,WANG Ye.Intramolecular Charge Transfer and Intermolecular Multiple Proton Transfer Mechanism of 7-Hydroxyflavone in Water[J].Journal of Jilin University(Science Edition),2017,55(5):1317-1322.)
[7]WANG Ye,SHI Ying,CONG Lin,et al.TDDFT Study of Twisted Intramolecular Charge Transfer and Intermolecular Double Proton Transfer in the Excited State of 4′-Dimethylaminoflavonol in Ethanol Solvent[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2015,137:913-918.
[8]AHLRICHS R,BAR M,HASER M,et al.Electronic Structure Calculations on Workstation Computers:The Program System Turbomole[J].Chemical Physics Letters,1989,162(3):165-169.
[9]VAHTRAS O,ALMLOF J,FEYEREISEN M W.Integral Approximations for LCAO-SCF Calculations[J].Chemical Physics Letters,1993,213(5/6):514-518.
[10]SCHAFER A,HUBER C,AHLRICHS R.Fully Optimized Contracted Gaussian Basis Sets of Triple Zeta Valence Quality for Atoms Li to Kr[J].The Journal of Chemical Physics,1994,100(8):5829-5835.
[11]WHITTEN J L.Coulombic Potential Energy Integrals and Approximations[J].The Journal of Chemical Physics,1973,58(10):4496-4501.
[12]王野,辛春雨,罗香怡.1-羟基-2-萘甲醛分子基态和激发态的质子转移机制[J].吉林大学学报(理学版),2017,55(6):1582-1586.(WANG Ye,XIN Chunyu,LUO Xiangyi.Proton Transfer Mechanism of Ground State and Excited State of 1-Hydroxy-2-naphthaldehyde Molecule[J].Journal of Jilin University(Science Edition),2017,55(6):1582-1586.)
[13]LAURENT A D,JACQUEMIN D.TD-DFT Benchmarks:A Review[J].International Journal of Quantum Chemistry,2013,113(17):2019-2039.
[14]WANG Ye,LI Hui,SHI Ying.Evidence for Hydrogen-Bonded Ammonia Wire Influence the ESMPT Process of7-Hydroxy-4-methylcoumarin·(NH3)3Cluster[J].New Journal of Chemistry,2015,39(9):7026-7032.
[15]ZHAO Guangjiu,HAN Keli.Effects of Hydrogen Bonding on Tuning Photochemistry:Concerted Hydrogen-Bond Strengthening and Weakening[J].Chemphyschem,2008,9(13):1842-1846.
[16]ZHAO Guangjiu,HAN Keli.Hydrogen Bonding in the Electronic Excited State[J].Accounts of Chemical Research,2012,45(3):404-413.
[2]余江虹,原鲜霞,贾超,等.氨基喹啉及其衍生物的性质、合成和应用[J].化学世界,2009(2):122-126.(YU Jianghong,YUAN Xianxia,JIA Chao,et al.Property,Synthesis and Application of Aminoquinoline Series[J].Chemistry World,2009(2):122-126.)
[3]JIA Xueli,LI Chaozheng,LI Donglin,et al.TDDFT Study on Excited State Intramolecular Proton Transfer Mechanism in 2-Amino-3-(2′-benzazolyl)-quinolines[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2018,192:168-173.
[4]KHIMICH M N,IVANOV V L,MEL’NIKOV M Y,et al.Peculiarities of Exited State Intramolecular Proton Transfer in 2-Amino-3-(2′-benzazolyl)-quinolines[J].High Energy Chemistry,2017,51(1):17-23.
[5]WANG Ye,YIN Hang,SHI Ying,et al.Ground-State and Excited-State Multiple Proton Transfer via a Hydrogen-Bonded Water Wire for 3-Hydroxypyridine[J].New Journal of Chemistry,2014,38(9):4458-4464.
[6]辛春雨,王野.7-羟基黄酮分子在水中分子内电荷转移及分子间多重质子的转移机制[J].吉林大学学报(理学版),2017,55(5):1317-1322.(XIN Chunyu,WANG Ye.Intramolecular Charge Transfer and Intermolecular Multiple Proton Transfer Mechanism of 7-Hydroxyflavone in Water[J].Journal of Jilin University(Science Edition),2017,55(5):1317-1322.)
[7]WANG Ye,SHI Ying,CONG Lin,et al.TDDFT Study of Twisted Intramolecular Charge Transfer and Intermolecular Double Proton Transfer in the Excited State of 4′-Dimethylaminoflavonol in Ethanol Solvent[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2015,137:913-918.
[8]AHLRICHS R,BAR M,HASER M,et al.Electronic Structure Calculations on Workstation Computers:The Program System Turbomole[J].Chemical Physics Letters,1989,162(3):165-169.
[9]VAHTRAS O,ALMLOF J,FEYEREISEN M W.Integral Approximations for LCAO-SCF Calculations[J].Chemical Physics Letters,1993,213(5/6):514-518.
[10]SCHAFER A,HUBER C,AHLRICHS R.Fully Optimized Contracted Gaussian Basis Sets of Triple Zeta Valence Quality for Atoms Li to Kr[J].The Journal of Chemical Physics,1994,100(8):5829-5835.
[11]WHITTEN J L.Coulombic Potential Energy Integrals and Approximations[J].The Journal of Chemical Physics,1973,58(10):4496-4501.
[12]王野,辛春雨,罗香怡.1-羟基-2-萘甲醛分子基态和激发态的质子转移机制[J].吉林大学学报(理学版),2017,55(6):1582-1586.(WANG Ye,XIN Chunyu,LUO Xiangyi.Proton Transfer Mechanism of Ground State and Excited State of 1-Hydroxy-2-naphthaldehyde Molecule[J].Journal of Jilin University(Science Edition),2017,55(6):1582-1586.)
[13]LAURENT A D,JACQUEMIN D.TD-DFT Benchmarks:A Review[J].International Journal of Quantum Chemistry,2013,113(17):2019-2039.
[14]WANG Ye,LI Hui,SHI Ying.Evidence for Hydrogen-Bonded Ammonia Wire Influence the ESMPT Process of7-Hydroxy-4-methylcoumarin·(NH3)3Cluster[J].New Journal of Chemistry,2015,39(9):7026-7032.
[15]ZHAO Guangjiu,HAN Keli.Effects of Hydrogen Bonding on Tuning Photochemistry:Concerted Hydrogen-Bond Strengthening and Weakening[J].Chemphyschem,2008,9(13):1842-1846.
[16]ZHAO Guangjiu,HAN Keli.Hydrogen Bonding in the Electronic Excited State[J].Accounts of Chemical Research,2012,45(3):404-413.