卤素替换构筑环亮氨酸冠醚型超分子相变材料及其性能研究  

Properties reasearch of cycloleucine crown ether type supramolecular phase transition materials constructed by halogen substitution

作　　者：王娜[1] 胡宏志 余炳德 刘洋[1,2,3] 刘尊奇[1,2,3] WANG Na;HU Hong-zhi;YU Bing-de;LIU Yang;LIU Zun-qi(College of Chemistry and Chemical Engineering Xinjiang Agricultural University,Urumqi 830052,China;Xinjiang Key Laboratory of Agricultural Chemistry and Biomaterials,Urumqi 830052,China;Xinjiang Branch of National Engineering Research Center for New Polymer Forming Equipment,Urumqi 830052,China)

机构地区：[1]新疆农业大学化学化工学院,新疆乌鲁木齐830052 [2]聚合物新型成型装备国家工程研究中心新疆分中心,新疆乌鲁木齐830052 [3]新疆农业化学与生物材料重点实验室,新疆乌鲁木齐830052

出　　处：《化学研究与应用》2025年第4期799-813,共15页Chemical Research and Application

基　　金：新疆维吾尔自治区自然科学基金面上项目(2022D01A76)资助;新疆维吾尔自治区重点研发专项(20220264-3)资助;新疆农业化学与生物材料重点实验室开放课题基金资助项目(KF202206)资助;国家自然科学基金(21561030)资助;新疆“天山英才”计划项目资助;新疆农业大学大学生创新项目(dxscx2024223)资助。

摘　　要：本文通过Cl/Br卤素替换,选用客体环亮氨酸和主体18-冠醚-6设计并构筑两种冠醚型包合物(C_(7)H_(14)NO_(2))^(+)(18-crown-6)[FeCl_(4)]^(-)(1)和(C_(7)H_(14)NO_(2))^(+)(18-crown-6)[FeBr_(4)]^(-)(2)。并采用红外光谱(IR)、X-射线单晶衍射、X-射线粉末衍射(XRD)、热重(TG)、赫什菲尔德曲面分析(Hirshfeld surface analysis)、介电以及循环伏安曲线测试等多种方式对其化合物进行表征。结构解析显示在低温(100 K)和室温(293 K)条件下,化合物均属于单斜晶系,空间群为P21/c。材料内甲酯化环亮氨酸阳离子与18-冠醚-6分子呈现分子内转子-定子结构。卤素原子替换导致无机阴离子无序、18-冠醚-6分子无序-有序运动及甲酯化环亮氨酸阳离子分子动态摆动,引起材料呈现良好的电催化性能,尤其化合物2在230 K和250 K附近表现出良好的连续可逆热能相变及连续可逆介电异常,显示其为新型具有电催化-介电循环可逆型多功能晶体材料。Two crown ether clathrates(C_(7)H_(14)NO_(2))^(+)(18-crown-6)[FeCl_(4)]^(-)(1)and(C_(7)H_(14)NO_(2))^(+)(18-crown-6)[FeBr_(4)]^(-)(2)were designed and constructed by using guest cycloleucine and subject 18-crown-6 through Cl/Br halogen substitution.The two compounds were characterized by infrared spectroscopy(IR),X-ray single crystal diffraction,X-ray powder diffraction(XRD),thermogravimetric(TG),Hirshfeld surface analysis,dielectric,cyclic voltammetry tests and so on.X-ray single crystal structure analysis shows that compounds belong to monoclinic crystal system and the space group is P2_(1)/c.The methyl esterized cycloleucine cations and 18-crown-6 molecules showed intramolecular rotor-stator structure in the materials.The substitution of halogen atoms result in inorganic anions disorder,order-disorder motion of 18-crown-6 molecules and methyl esterized cycloleucine cationic molecules oscillate dynamically.This leads to the material showed good electrocatalytic performance.Two pairs of endothermic/exothermic peaks(230/246 K and 263/257 K)appeared during cooling and heating of induced compound 2 under external temperature stimulation,indicating two successive structural phase transitions.In particular,compound 2 displays good continuous reversible thermal phase transition and continuous reversible dielectric anomaly around 230 K and 250 K,revealing it is a new type of electrocatalytic-dielectric cycle reversible multifunctional crystal material.

关 键 词：卤素替换 甲酯化环亮氨酸 18-冠醚-6 相变材料 介电性质 

分 类 号：O611.2[理学—无机化学]