基于咪唑阳离子的双离子氢键理论研究
发布时间：2018-10-30 08:32
【摘要】：1、离子液体以其独特的性质及广泛的应用吸引了人们的注意。而氢键作为离子液体中一种重要的非共价作用,其数量与强弱将影响离子液体的性质。因此本文将使用量子化学的计算方法对两种咪唑类阳离子(一甲基咪唑阳离子[Mim]+、1,3-二甲基咪唑阳离子[Mmim]+)及不同的阴离子([NO3]-、[ClO4]-、[BF4]-、[AlCl4]-、[Al2Cl7]-)结合形成的离子对及氢键进行研究。(1)在MP2/6-311++G(d,p)理论水平上对一甲基咪唑[Mim]+类复合物([Mim]+[NO3]-、[Mim]+[ClO4]-、[Mim]+[BF4]-、[Mim]+[AlCl4]-、[Mim]+[Al2Cl7]-)进行结构优化及性质计算。通过对这些复合物进行结构分析、相互作用能比较、自然键轨道(NBO)中的二阶微扰能分析、电荷转移量比较、分子中的原子(AIM)分析,结果表明:a.所有的阴阳离子对之间都发生了电荷转移,证明阴、阳离子之间形成氢键。b.通过对离子对中形成的氢键的平衡距离、二阶微扰能E(2)及AIM进行分析和比较,结果表明:质子性的NH···X氢键的强度强于非质子性的CH···X氢键。c.正负离子间的总相互作用能变化趋势与氢键强弱的顺序是一致的,[Mim]+[NO3]-[Mim]+[ClO4]-[Mim]+[BF4]-[Mim]+[AlCl4]-。d.阴离子从侧面接触[Mim]+形成的”side”构象比从上面接触形成的“top”构象更利于氢键的形成。(2)在MP2/6-311++G(d,p)理论水平上对1,3-二甲基咪唑[Mmim]+类复合物([Mmim]+[NO3]-、[Mmim]+[ClO4]-、[Mmim]+[BF4]-、[Mmim]+[AlCl4]-、[Mim]+[Al2Cl7]-)进行结构优化及相互作用能计算。通过与一系列的一甲基咪唑[Mim]+类复合物进行对比,结果表明:a.1,3-二甲基咪唑[Mmim]+类复合物的氢键均比相应的一甲基咪唑[Mim]+类复合物氢键弱,这是因为缺少质子性的N-H键的存在。b.[Mmim]+[AlCl4]-的稳定构型及相互作用能和化合物[Mmim]+[Al2Cl7]-的很形似,这与[Mim]+[AlCl4]-和[Mim]+[Al2Cl7]-的结论类似。c.氢键强弱顺序为[Mmim]+[NO3]-[Mmim]+[ClO4]-[Mmim]+[BF4]-[Mmim]+[AlCl4]-,与一甲基咪唑[Mim]+类复合物结论一致。2、本文采用密度泛函理论(DFT),在B3LYP/6-311++G(d,p)理论水平上并结合D3校正研究了不同的阳离子([Mim]+、[Mmim]+)和阴离子([NO3]-、[ClO4]-、[BF4]-、[AlCl4]-、[Al2Cl7]-)及离子对([Mim]+[ClO4]-、[Mmim]+[NO3]-)分别与SO2分子形成复合物的几何构型及相互作用能。结果表明:SO2与[Mim]+形成一个N-H···O-S和一个C-H···O-S型氢键,而与[Mmim]+形成两个C-H···O-S型氢键,两者作用能相差约14kJ·mol-1。SO2与阴离子NO3-、ClO4-、BF4-、AlCl4-之间通过O-Sδ+···Xδ-型的静电引力结合,作用力介于38~90 kJ·mol-1。结果表明SO2与阳离子间的C-H···O-S型氢键及与阴离子间的静电引力是咪唑阳离子类离子液体脱硫效果的主要来源。
[Abstract]:1. Ionic liquids have attracted much attention for their unique properties and wide applications. As an important noncovalent interaction in ionic liquids, the amount and strength of hydrogen bonds will affect the properties of ionic liquids. Therefore, two kinds of imidazole cations (Mim, Mmim) and different anions ([NO3] -, [ClO4] -, [BF4] -) and different anions ([NO3] -, [ClO4] -, [BF4] -) are calculated by quantum chemistry. [AlCl4] -, [Al2Cl7] -) binding ion pairs and hydrogen bonds were studied. (1) at the theoretical level of MP2/6-311 G (DNP), the complexes of [Mim] [Mim] class ([Mim] [NO3] -], [Mim] [ClO4] -, [Mim] [BF4] -, [Mim] [AlCl4] -, [Mim] [Al2Cl7] -) for structural optimization and properties calculation. By analyzing the structure of these complexes, comparing the interaction energy, analyzing the second order perturbation energy in the natural bond orbital (NBO), comparing the charge transfer amount, and analyzing the atomic (AIM) in the molecule, the results show that: a. Charge transfer occurs between all pairs of anions and cations, proving that hydrogen bonds are formed between anions and cations. The equilibrium distance of hydrogen bond formed in ion pair, second order perturbation energy E (2) and AIM were analyzed and compared. The results show that the strength of proton NH X hydrogen bond is stronger than that of non proton CH X hydrogen bond. The change trend of total interaction energy between positive and negative ions is consistent with the order of hydrogen bond strength, [Mim] [NO3]-[Mim] [ClO4]-[Mim] [BF4]-[Mim] [AlCl4] -. The "side" conformation formed by the side contact of anions [Mim] is more favorable to the formation of hydrogen bonds than the "top" conformation formed from the above contact. (2) in MP2/6-311 G (d, the formation of hydrogen bonds is more favorable. P) at the theoretical level, the complexes of [Mmim] [NO3] -, [Mmim] [ClO4] -, [Mmim] [BF4] -, [Mmim] [AlCl4]- [Mim] [Al2Cl7] -) structure optimization and interaction energy calculation. Compared with a series of monomethyl imidazole [Mim] complexes, the results show that the hydrogen bonds of A. 1 and 3-dimethyl imidazole [Mmim] complexes are weaker than those of the corresponding Mim complexes. This is due to the absence of proton N-H bonds. The stable configuration and interaction energy of [Mmim] [AlCl4]-is similar to that of compound [Mmim] [Al2Cl7]. This is similar to the conclusion of [Mim] [AlCl4]-and [Mim] [Al2Cl7]. The order of hydrogen bond strength is [Mmim] [NO3]-[Mmim] [ClO4]-[Mmim] [BF4]-[Mmim] [AlCl4] -, which is consistent with the conclusion of a methylimidazole [Mim] class complex. 2. The density functional theory (DFT) (DFT), is used in this paper. Different cations ([Mim], [Mmim]) and anions ([NO3] -, [ClO4] -, [BF4] -, [AlCl4] -, [BF4] -, [AlCl4] -] have been studied at the theoretical level of B3LYP/6-311 G (DNP) and D3 correction. [Al2Cl7] -) and [Mim] [ClO4] -, [Mmim] [NO3] -, respectively. The results show that SO2 forms a N-H O-S and C-H O-S hydrogen bonds with [Mim] and two C-H O-S hydrogen bonds with [Mmim]. The difference of the interaction energy between 14kJ mol-1.SO2 and anionic NO3-,ClO4-,BF4-,AlCl4- is about the interaction of O-S 未 X 未-type electrostatic force between NO3-,ClO4-,BF4-,AlCl4- and O-S 未, and the interaction force is between 38 kJ mol-1. and 90 kJ mol-1.. The results show that the C-H O-S hydrogen bond between SO2 and cations and the electrostatic force between SO2 and anions are the main sources of desulfurization effect of imidazole cationic ionic liquids.
【学位授予单位】：山西师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.1
本文编号：2299491
[Abstract]:1. Ionic liquids have attracted much attention for their unique properties and wide applications. As an important noncovalent interaction in ionic liquids, the amount and strength of hydrogen bonds will affect the properties of ionic liquids. Therefore, two kinds of imidazole cations (Mim, Mmim) and different anions ([NO3] -, [ClO4] -, [BF4] -) and different anions ([NO3] -, [ClO4] -, [BF4] -) are calculated by quantum chemistry. [AlCl4] -, [Al2Cl7] -) binding ion pairs and hydrogen bonds were studied. (1) at the theoretical level of MP2/6-311 G (DNP), the complexes of [Mim] [Mim] class ([Mim] [NO3] -], [Mim] [ClO4] -, [Mim] [BF4] -, [Mim] [AlCl4] -, [Mim] [Al2Cl7] -) for structural optimization and properties calculation. By analyzing the structure of these complexes, comparing the interaction energy, analyzing the second order perturbation energy in the natural bond orbital (NBO), comparing the charge transfer amount, and analyzing the atomic (AIM) in the molecule, the results show that: a. Charge transfer occurs between all pairs of anions and cations, proving that hydrogen bonds are formed between anions and cations. The equilibrium distance of hydrogen bond formed in ion pair, second order perturbation energy E (2) and AIM were analyzed and compared. The results show that the strength of proton NH X hydrogen bond is stronger than that of non proton CH X hydrogen bond. The change trend of total interaction energy between positive and negative ions is consistent with the order of hydrogen bond strength, [Mim] [NO3]-[Mim] [ClO4]-[Mim] [BF4]-[Mim] [AlCl4] -. The "side" conformation formed by the side contact of anions [Mim] is more favorable to the formation of hydrogen bonds than the "top" conformation formed from the above contact. (2) in MP2/6-311 G (d, the formation of hydrogen bonds is more favorable. P) at the theoretical level, the complexes of [Mmim] [NO3] -, [Mmim] [ClO4] -, [Mmim] [BF4] -, [Mmim] [AlCl4]- [Mim] [Al2Cl7] -) structure optimization and interaction energy calculation. Compared with a series of monomethyl imidazole [Mim] complexes, the results show that the hydrogen bonds of A. 1 and 3-dimethyl imidazole [Mmim] complexes are weaker than those of the corresponding Mim complexes. This is due to the absence of proton N-H bonds. The stable configuration and interaction energy of [Mmim] [AlCl4]-is similar to that of compound [Mmim] [Al2Cl7]. This is similar to the conclusion of [Mim] [AlCl4]-and [Mim] [Al2Cl7]. The order of hydrogen bond strength is [Mmim] [NO3]-[Mmim] [ClO4]-[Mmim] [BF4]-[Mmim] [AlCl4] -, which is consistent with the conclusion of a methylimidazole [Mim] class complex. 2. The density functional theory (DFT) (DFT), is used in this paper. Different cations ([Mim], [Mmim]) and anions ([NO3] -, [ClO4] -, [BF4] -, [AlCl4] -, [BF4] -, [AlCl4] -] have been studied at the theoretical level of B3LYP/6-311 G (DNP) and D3 correction. [Al2Cl7] -) and [Mim] [ClO4] -, [Mmim] [NO3] -, respectively. The results show that SO2 forms a N-H O-S and C-H O-S hydrogen bonds with [Mim] and two C-H O-S hydrogen bonds with [Mmim]. The difference of the interaction energy between 14kJ mol-1.SO2 and anionic NO3-,ClO4-,BF4-,AlCl4- is about the interaction of O-S 未 X 未-type electrostatic force between NO3-,ClO4-,BF4-,AlCl4- and O-S 未, and the interaction force is between 38 kJ mol-1. and 90 kJ mol-1.. The results show that the C-H O-S hydrogen bond between SO2 and cations and the electrostatic force between SO2 and anions are the main sources of desulfurization effect of imidazole cationic ionic liquids.
【学位授予单位】：山西师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.1
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