【作者】 陆国栋；

【导师】 姚加；

【作者基本信息】 浙江大学 ， 化学， 2019， 硕士

【摘要】 本文通过对金属螯合型离子液体的物理性质和单晶结构的探究,研究了不同中心金属对离子液体的物性和结构影响。金属螯合型离子液体兼具配合物和离子液体的性质,有潜在的应用价值。但关于这部分的物性研究工作目前还有限,本文主要着重于金属螯合型离子液体物性和结构两个方面来描述其特点,并尝试关联物性和结构以解释物性之间的差异。本文合成了三种不同金属的螯合型离子液体[C1()mim][M(hfac)3](M=Co,Ni,Cu),并通过重复萃取进行纯化。在(328.15-343.15)K下测量了密度和黏度,在(323.15-343.15)K.测量了电导率和表面张力,同时还测定了熔点。对比实验数据,三种金属的螯合型离子液体密度和熔点相差较小,黏度和电导率差别较大,表面张力基本一致。根据Glasser公式计算了离子液体的晶格能并估算了标准摩尔熵;使用Kabo法估算了离子液体的标准摩尔蒸发焓;使用Walden规则对比了三种离子液体的离子性,发现三者之间相差较小。由于包含较大的阴离子,对比常规离子液体的物性,金属螯合型离子液体拥有较大的分子体积,较高的黏度,较低的晶格能、电导率和表面张力。培养了不同金属和链长的金属螯合型离子液体的单晶,通过X射线晶体衍射确定其结构,对比不同离子液体的单晶构型,发现晶格内部的氢键作用方式差异较大。依据似晶格理论将液态结构与单晶结构两者联系起来,以单晶作为出发点,讨论离子液体液态下近程有序的堆积性质,结合物性数据,通过分析晶胞堆积内部的氢键作用方式来解释离子液体不同链长和金属带来的物性差异。更多还原

【Abstract】 In this paper,the physical properties and single crystal structure of chelate-based metal containing ionic liquids(ChILs)were studied.ChILs possess properties of both complexes and ionic liquids(ILs)and have potential application in many fields.However,researches focused on the physical properties of ChILs are still limited at present.This paper mainly focused on the physical properties and structure of ChILs to describe their characteristics and attempted to explain the differences between properties by associating the physical properties and structure.Three ChILs of different metals[C10mim][M(hfac)3](M = Co,Ni,Cu)have been synthesized and purified by repeated extraction.Densities and viscosities were measured in the temperature range(328.15-343.15)K,conductivities and surface tensions were measured in the temperature range(323.15-343.15)K,and melting points were also determined.Compared with the experimental data,three ChILs have smaller differences in density and melting point,larger differences in viscosity and conductivity and the surface tensions are basically the same.The lattice energies of ChILs were calculated according to Glasser formula and the standard molar entropies were also estimated.The molar enthalpies of evaporation of ChILs were estimated by Kabo’s method.Walden rule was used to compare the ionicity of the three ChILs and it was found that the differences among three ChILs were relatively small.Compared with the physical properties of conventional ionic liquids,ChILs have a larger molecular volume,higher viscosity,lower lattice energy,conductivity and surface tension as the existence of large anions.Single crystals of ChILs were prepared and the structures were determined by X-ray crystal diffraction.Compared with different single crystal configurations,it was found that the hydrogen-bond interaction in the lattice is quite different.Based on the quasi-lattice theory,liquid and single crystal structure were connected.Taking single crystal as the starting point,the short-range ordered stacking of the ionic liquid were discussed.In combination with the physical properties data,the differences caused by the different chain lengths and metals of the ChILs were explained by analyzing the hydrogen-bond interaction inside the unit cell.更多还原