缩酮席夫碱类阴离子识别的量子化学研究
|
摘要
缩酮席夫碱是良好的阴离子识别剂,利用量子化学密度泛函理论研究了3种缩酮席夫碱阴离子受体与阴离子客体相结合的空间结构、电荷分布、结合能等方面的变化,计算结果表明,阴离子受体分子的阴离子结合位点位于亚氨基-NH-部,受体分子和阴离子间通过氢键相互作用,阴离子有一部分负电荷转移到受体分子中,且转移的电荷量为R3-3> R3-2> R3-1,在考察的阴离子中,F~-与受体分子的结合能最大,而在3种受体分子中,R3-3对阴离子结合能最大.计算模拟结果,与实验情况相吻合.
Ketal Schiff Base is a good anion recognition agent, density functional theory was used to investigate the spatial structure, charge distribution, binding energy and other changes in the combination of three Ketal Schiff Base Anions receptors with anionic guest. The calculated results show that the anionic binding site of the anion acceptor molecule is located in the imino-NH-moiety, the hydrogen bond interaction between the acceptor molecule and the anion leads to the negative charge transfer of the anion to the acceptor molecule, and the amount of charge transferred is R3-3 > R3-2 > R3-1, in the investigated anions, the binding energy of F~- to the acceptor molecule is the highest, while among the three acceptor molecules, R3-3 has the highest binding energy to the anion. The simulation results are in agreement with the experimental conditions.
Ketal Schiff Base is a good anion recognition agent, density functional theory was used to investigate the spatial structure, charge distribution, binding energy and other changes in the combination of three Ketal Schiff Base Anions receptors with anionic guest. The calculated results show that the anionic binding site of the anion acceptor molecule is located in the imino-NH-moiety, the hydrogen bond interaction between the acceptor molecule and the anion leads to the negative charge transfer of the anion to the acceptor molecule, and the amount of charge transferred is R3-3 > R3-2 > R3-1, in the investigated anions, the binding energy of F~- to the acceptor molecule is the highest, while among the three acceptor molecules, R3-3 has the highest binding energy to the anion. The simulation results are in agreement with the experimental conditions.
引文
[1] Geng W H,Wang Y R,Li X,et al.DFT study on anion receptors based on urea and thiourea derivatives [J].Chem.Res.,2017,28:1 (in Chinese) [耿玮宏,王亚茹,李夏,等.DFT方法研究基于脲及硫脲衍生物的阴离子受体[J].化学研究,2017,28:1]
[2] Dominika Z,Joanna K,Piotr P T.Exploiting cooperative binding of ion-pair to boost anion recognition in water/acetonitrile mixtures [J].Tetrahedron.,2017,73:719.
[3] Sebastian A R,Dieter S,Maximilinf F,et al.Optical sensing of anions via supramolecular recognition with biimidazole complexes [J].Chem.Eur.J.,2017,23:18101.
[4] Li Z,Yu X H,Chen Y,et al.Synthesis,anion recognition,and transmembrane anionophoric activity of tripodal diaminocholoyl conjugates [J].J.Org.Chem.,2017,82:13368.
[5] Jia B L.Progress in quantum chemistry calculation [J].Sci.Tech.Inno.Herald.,2013,36:14 (in Chinese) [贾宝丽.量子化学计算研究进展[J].科技创新导报,2013,36:14]
[6] Li C X,Li L,Wang C,et al.Study of the protection performance of self-assembled monolayers on copper with the scanning electrochemical microscope [J].Corros.Sci.,2014,80:511.
[7] Zhang F L.Density functional theory study of the structures and activityies for pyrrolpyrazole compounds [J].J.At.Mol.Phys.,2018,35:7 (in Chinese) [张福兰.吡唑联吡咯类化合物结构和活性的密度泛函理论研究[J].原子与分子物理学报,2018,35:7]
[8] Qi W S,Wang H F,Li Q.Studies on spectra and thermodynamic properties of dual prenylated flavonoids [J].J.Sichuan Univ.:Nat.Sci.Ed.,2016,53:389 ( in Chinese) [漆文胜,王海峰,李权.双异戊烯基黄酮分子的光谱和热力学性质研究[J].四川大学学报:自然科学版,2016,53:389]
[9] Sun T T,Huang J,He W P,et al.Density functional study of norfloxacin [J].J.Sichuan Univ.:Nat.Sci.Ed.,2017,54:1049 (in Chinese) [孙婷婷,黄菊,何伟平,等.诺氟沙星的密度泛函研究[J].四川大学学报:自然科学版,2017,54:1049]
[10] Cui Y,Chen J C,Yu J Y,et al.A DFT study on structure change of [Ru(bpy)2]2+(L=H2biim,H2bbim) as anions sensors after deprotonation [J].J.Mol.Sci.,2012,28:1 (in Chinese) [崔英,陈锦灿,于志瀛,等.DFT研究阴离子识别剂[Ru(bpy)2L]2+(L = H2biim,H2bbim)去质子后结构变化[J].分子科学学报,2012,28:1]
[11] Pan G X,Ni Z M,Wang L G,et al.A DFT Study on supramolecular interaction between halide anion and o-Di(pyrrolyl-2-formamido)phenylene in DMSO [J].Acta Chim.Sin.,2007,21:2377 (in Chinese) [潘国祥,倪哲明,王力耕,等.密度泛函理论研究DMSO溶剂中邻-二(吡咯-2-甲酰胺基)亚苯与卤素阴离子间的超分子作用[J].化学学报,2007,21:2377]
[12] Zhang F L.Density functional theory study of the structure and activity for 2,3-disubstituted quinazolin-4(3H) [J].J.At.Mol.Phys.(原子与分子物理学报),2016,33:415 (in Chinese)
[13] Mustafa T B,Senay Y,Zeynep D,et al.Crystal structure,FT-IR,FT-Raman and DFT studies on a novel compound [C10H9N3]4AgNO3[J].J.Organ.Chem.,2016,805:108.
[14] Yang F,Wang H F,Li Q.Computational study of molecular spectra and thermodynamic properties of two kinds of azulene sulfonamide schiff base derivatives [J].J.At.Mol.Phys.(原子与分子物理学报),2016,33:575 (in Chinese)
[15] Li S S,Kang J,Cao X F,et al.Acylthiourea derivatives as colorimetric sensors for anions:synthesis,characterization and spectral behaviors [J].Spectrochim.Acta.A,2016,153:471.
[16] Mardanya S,Karmakar S,Das S,et al.Anion and cation triggered modulation of optical properties of a pyridyl-imidazole receptor rigidly linked to pyrene and construction of INHIBIT,OR and XOR molecular logic gates:A combined experimental and DFT/TD-DFT investigation [J].Sensor Actuat.B Chem.,2015,206:701.
[17] Li G Y,Zhao G J,Liu Y H,et al.TD-DFT study on the sensing mechanism of a fluorescent chemosensor for fluoride:excited-state proton transfer [J].J.Comput.Chem.,2010,31:1759.
[18] Zapata F,Caballero A,White N G,et al.Fluorescent charge-assisted halogen-bonding macrocyclic haloImidazolium receptors for anion recognition and sensing in aqueous media [J].J.Am.Chem.Soc.,2012,134:11533.
[19] Li G Y,Zhao G J,Han K L,et al.A TD-DFT Study on the cyanide-chemosensing mechanism of 8-formyl-7-hydroxycoumarin [J].J.Comput.Chem.,2011,32:668.
[20] Zhao J Y,Zhang Y,Li R Q,et al.Theoretical studies on the preferential binding of anions to a benzimidazole based anion receptor [J].Pol.J.Chem.,2009,83:651.
[2] Dominika Z,Joanna K,Piotr P T.Exploiting cooperative binding of ion-pair to boost anion recognition in water/acetonitrile mixtures [J].Tetrahedron.,2017,73:719.
[3] Sebastian A R,Dieter S,Maximilinf F,et al.Optical sensing of anions via supramolecular recognition with biimidazole complexes [J].Chem.Eur.J.,2017,23:18101.
[4] Li Z,Yu X H,Chen Y,et al.Synthesis,anion recognition,and transmembrane anionophoric activity of tripodal diaminocholoyl conjugates [J].J.Org.Chem.,2017,82:13368.
[5] Jia B L.Progress in quantum chemistry calculation [J].Sci.Tech.Inno.Herald.,2013,36:14 (in Chinese) [贾宝丽.量子化学计算研究进展[J].科技创新导报,2013,36:14]
[6] Li C X,Li L,Wang C,et al.Study of the protection performance of self-assembled monolayers on copper with the scanning electrochemical microscope [J].Corros.Sci.,2014,80:511.
[7] Zhang F L.Density functional theory study of the structures and activityies for pyrrolpyrazole compounds [J].J.At.Mol.Phys.,2018,35:7 (in Chinese) [张福兰.吡唑联吡咯类化合物结构和活性的密度泛函理论研究[J].原子与分子物理学报,2018,35:7]
[8] Qi W S,Wang H F,Li Q.Studies on spectra and thermodynamic properties of dual prenylated flavonoids [J].J.Sichuan Univ.:Nat.Sci.Ed.,2016,53:389 ( in Chinese) [漆文胜,王海峰,李权.双异戊烯基黄酮分子的光谱和热力学性质研究[J].四川大学学报:自然科学版,2016,53:389]
[9] Sun T T,Huang J,He W P,et al.Density functional study of norfloxacin [J].J.Sichuan Univ.:Nat.Sci.Ed.,2017,54:1049 (in Chinese) [孙婷婷,黄菊,何伟平,等.诺氟沙星的密度泛函研究[J].四川大学学报:自然科学版,2017,54:1049]
[10] Cui Y,Chen J C,Yu J Y,et al.A DFT study on structure change of [Ru(bpy)2]2+(L=H2biim,H2bbim) as anions sensors after deprotonation [J].J.Mol.Sci.,2012,28:1 (in Chinese) [崔英,陈锦灿,于志瀛,等.DFT研究阴离子识别剂[Ru(bpy)2L]2+(L = H2biim,H2bbim)去质子后结构变化[J].分子科学学报,2012,28:1]
[11] Pan G X,Ni Z M,Wang L G,et al.A DFT Study on supramolecular interaction between halide anion and o-Di(pyrrolyl-2-formamido)phenylene in DMSO [J].Acta Chim.Sin.,2007,21:2377 (in Chinese) [潘国祥,倪哲明,王力耕,等.密度泛函理论研究DMSO溶剂中邻-二(吡咯-2-甲酰胺基)亚苯与卤素阴离子间的超分子作用[J].化学学报,2007,21:2377]
[12] Zhang F L.Density functional theory study of the structure and activity for 2,3-disubstituted quinazolin-4(3H) [J].J.At.Mol.Phys.(原子与分子物理学报),2016,33:415 (in Chinese)
[13] Mustafa T B,Senay Y,Zeynep D,et al.Crystal structure,FT-IR,FT-Raman and DFT studies on a novel compound [C10H9N3]4AgNO3[J].J.Organ.Chem.,2016,805:108.
[14] Yang F,Wang H F,Li Q.Computational study of molecular spectra and thermodynamic properties of two kinds of azulene sulfonamide schiff base derivatives [J].J.At.Mol.Phys.(原子与分子物理学报),2016,33:575 (in Chinese)
[15] Li S S,Kang J,Cao X F,et al.Acylthiourea derivatives as colorimetric sensors for anions:synthesis,characterization and spectral behaviors [J].Spectrochim.Acta.A,2016,153:471.
[16] Mardanya S,Karmakar S,Das S,et al.Anion and cation triggered modulation of optical properties of a pyridyl-imidazole receptor rigidly linked to pyrene and construction of INHIBIT,OR and XOR molecular logic gates:A combined experimental and DFT/TD-DFT investigation [J].Sensor Actuat.B Chem.,2015,206:701.
[17] Li G Y,Zhao G J,Liu Y H,et al.TD-DFT study on the sensing mechanism of a fluorescent chemosensor for fluoride:excited-state proton transfer [J].J.Comput.Chem.,2010,31:1759.
[18] Zapata F,Caballero A,White N G,et al.Fluorescent charge-assisted halogen-bonding macrocyclic haloImidazolium receptors for anion recognition and sensing in aqueous media [J].J.Am.Chem.Soc.,2012,134:11533.
[19] Li G Y,Zhao G J,Han K L,et al.A TD-DFT Study on the cyanide-chemosensing mechanism of 8-formyl-7-hydroxycoumarin [J].J.Comput.Chem.,2011,32:668.
[20] Zhao J Y,Zhang Y,Li R Q,et al.Theoretical studies on the preferential binding of anions to a benzimidazole based anion receptor [J].Pol.J.Chem.,2009,83:651.