2,2’-二联吡啶及其配合物在电场作用下构象的理论研究
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摘要
为了考察电极界面中2,2’-二联吡啶(BP)分子的构象行为,利用类似现场量子化学计算方法,模拟了该分子在电场作用下的构象行为.利用不同基组考察了零电场下该分子随N-C_α-C_α’-N二面角变化的势能面.通过与高精度基组的数据比较,选择既保证计算精度,又可保证计算效率的HF/6-31G*方法,研究了不同强度点电荷构建的电场下,BP分子的扭转几何构象.从中得到高于4. 0 GV·m~(-1)的电场对于BP有很大的势能位阻.并用不同金属离子代替点电荷计算BP作为配体时的结合能,解释了其在无机配位结构中BP分子呈现平面构型的原因.
In order to understand the conformational behavior of 2,2'-bipyridine( BP) on the electrode interface,we simulate the conformational behavior of this molecule in an electric field by using quantum chemistry method. The potential energy surfaces of BP molecule are calculated by changing the dihedral angel of N-C_α-C_α'-N with different basis sets where field strength is zero. After comparing the data of the basis sets of high accuracy,HF/6-31G* is selected due to its relatively high precision and computational efficiency. The rotational potential energy surface of BP molecule in the electric field created by point charges of different strength have been computed with HF/6-31G* basis set. The rotational barrier increases dramatically when the strength of electric field is higher than 4. 0 GV·m~(-1). A series of metal cations are applied to replace the point charges to evaluate the binding energy of BP molecule as ligand so that the planar conformation of BP ligands in most inorganic coordination compounds could be explained.
In order to understand the conformational behavior of 2,2'-bipyridine( BP) on the electrode interface,we simulate the conformational behavior of this molecule in an electric field by using quantum chemistry method. The potential energy surfaces of BP molecule are calculated by changing the dihedral angel of N-C_α-C_α'-N with different basis sets where field strength is zero. After comparing the data of the basis sets of high accuracy,HF/6-31G* is selected due to its relatively high precision and computational efficiency. The rotational potential energy surface of BP molecule in the electric field created by point charges of different strength have been computed with HF/6-31G* basis set. The rotational barrier increases dramatically when the strength of electric field is higher than 4. 0 GV·m~(-1). A series of metal cations are applied to replace the point charges to evaluate the binding energy of BP molecule as ligand so that the planar conformation of BP ligands in most inorganic coordination compounds could be explained.
引文
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[20]HE Y,ZHANG J,ZHAO J. Electron Transport and CO Sensing Characteristics of Fe(II)Porphyrin with Single-Walled Carbon Nanotube Electrodes[J]. Journal of Physical Chemistry C,2014,118:18325-18333.
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[22]ZHAO J,UOSAKI K. Dielectric Properties of Organic Monolayers Directly Bonded on Silicon Probed by Current Sensing Atomic Force Microscope[J]. Appl. Phys. Lett. 2003,83:2034-2036.
[23]SAMANTA P,KRISHNA M. Leakage Current Conduction,Hole Injection,and Time-dependent Dielectric Breakdown of n-4H-SiC MOS Capacitors During Positive Bias Temperature Stress[J]. Journal of Applied Physics,2017,121(3):034501.
[24]徐仲,李宁,崔燕平,等.电场极化对碱基对质子转移和电子传递的影响[J].高等学校化学学报,2009,30(3):588-592.
[2]任颜卫,李珺,吴爱芝,等.混合价四核锰配合物[Mn4O2(CICH2COO)7(bipy)2]·H2O的合成、晶体结构及性质研究[J].化学学报,2005,63(10):919-923,871.
[3]王寿柏.吡啶和取代吡啶锌(Ⅱ)配合物中配键性质的研究[J].南通工学院学报,2001,17(3):48-50.
[4]ZHAO J. Conformational Analysis of 2,2’-Bithiophene under Interaction of External Electric Field Defined by Point Charges[J].Chem. Phys. Lett,2002,351:481-485.
[5]李延伟,章岩,尹鸽平,等.电场作用下分子导线的理论研究[J].高等学校化学学报,2006,27(2):292-296.
[6]ZHAO J,LI P,LI Y,et al. Theoretical Investigation on Conformational Behavior of 2,2’-Bithiophene under the Influence of External Electric Field at Ab Initio Levels[J]. J. Mol. Struct.(Theochem),2007,808:125-134.
[7]HOWARD S T. Conformers,Energetics,and Basicity of 2,2’-Bipyridine[J]. J. Am. Chem. Soc,1996,118(42):10269-10274.
[8]MERRITT L L JR,SCHROEDER E D. The crystal structure of 2,2’-bipyridine[J]. Acta. Crystallogr,1956,9:801-804.
[9]ALMENNINGEN A,BASTIANSEN O,GUNDERSEN S,et al. Structure and Barrier to Internal Rotation of Biphenyl Derivatives in the Gaseous State. Part 6 On the Molecular Structure and Internal Rotation of 2,2’-Bipyridine[J]. Lkartidningen, 1989,81(3):125-128.
[10]CHEN X,LIU L,MA J,et al. Synthesis,Reaction and Structure of a Series of Chromium(III)Complexes Containing Oxalate Ligand[J]. J. Molecular Structure.,2005,750:94-100.
[11]李君,张逢星,杨术明,等.双核锰配合物的合成、晶体结构及性质[J].科学通报,2000,45(1):36-39.
[12]KOPEL P,TRáVNíCEK Z,ZBORIL R,et al. Synthesis,X-ray and M9ssbauer Study of Iron(II)Complexes with Trithiocyanuric Acid[J]. Polyhedron,2004,23:2193-2202.
[13]张淑华,蒋毅民,张桂英,等.乙酸联吡啶合钴配合物的合成及晶体结构(英文)[J].广西师范大学学报(自然科学版),2004,22(4):53-56.
[14]韩峭峰,郝志峰,余坚,等.双核铜配合物[Cu2(pida)2(2,2’-bipy)2]的合成、表征及其结构[J].光谱实验室,2007,24(3):285-288
[15]XU Y,ZHOU Y,YUAN D,et al.Blue Luminescent Zinc(Ⅱ)-and Cadmium(Ⅱ)-1,4-phenylenediacetate Complexes[J].Chinese Journal of Structural Chemistry,2006,25(10):1161-1166.
[16] Li W,Li C,GUO D,et al. Synthesis,Crystal Structure and Electrochemical Properties of Complex[Ni(2,2’-bipy)2(ClC6H4COO)(H2O)](ClO4)][J]. Chinese Journal of Structural Chemistry,2006,25(4):387-391.
[17]RéGIS C,LéNA M,ALEXANDER T,et al. Efficient DNA Binding by Optically Pure Ruthenium Tris(bipyridyl)Complexes Incorporating Carboxylic Functionalities. Solution and Structural Analysis[J]. Inorg. Chem. 2004,43(25):7986-7993.
[18]俞马宏,靳松,杨绪杰,等.配体结构对钌(Ⅱ)联吡啶配合物的电子结构的影响[J].无机化学学报,1998,14(3):276-280.
[19]YIN X,LI Y,ZHANG Y,et al. Theoretical Analysis of Geometry-Correlated Conductivity of Molecular Wire[J]. Chem. Phys. Lett.2006,422:111-116.
[20]HE Y,ZHANG J,ZHAO J. Electron Transport and CO Sensing Characteristics of Fe(II)Porphyrin with Single-Walled Carbon Nanotube Electrodes[J]. Journal of Physical Chemistry C,2014,118:18325-18333.
[21]LIU H,WANG H,ZHAO J,et al. Molecular Rectification in the Asymmetric Graphene-based Nanoribbons[J]. Journal of Computational Chemistry,2013,34:360-365.
[22]ZHAO J,UOSAKI K. Dielectric Properties of Organic Monolayers Directly Bonded on Silicon Probed by Current Sensing Atomic Force Microscope[J]. Appl. Phys. Lett. 2003,83:2034-2036.
[23]SAMANTA P,KRISHNA M. Leakage Current Conduction,Hole Injection,and Time-dependent Dielectric Breakdown of n-4H-SiC MOS Capacitors During Positive Bias Temperature Stress[J]. Journal of Applied Physics,2017,121(3):034501.
[24]徐仲,李宁,崔燕平,等.电场极化对碱基对质子转移和电子传递的影响[J].高等学校化学学报,2009,30(3):588-592.
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