Crystal Structures,Thermal Analysis and Electrochemical Behaviors of Functionalized Pyridinium Ionic Liquids Comprising One 1-Ethyl Acetate Group |
| |
| Authors: | ZHAO Yamei CUI Hongmeng ZHENG Changzheng CHEN Xiaogang LI Chunyang |
| |
| Institution: | 1. Department of Chemical Engineering, School of Environment and Chemical Engineering, Xi'an Polytechnic University, Xi'an 710048, P. R. China;
2. School of Materials, the University of Manchester, Manchester, M13 9PL, UK |
| |
| Abstract: | Pyridinium ionic liquids(ILs, 1-ethyl acetate pyridinium hexfluorophosphateEAPy]PF6] and 1-ethyl acetate-3-methyl pyridinium hexfluorophosphateEAMPy]PF6]), were synthesized by a two-step process involving introduction of one ethyl acetate group and anion metathesis. Colorless single crystals of the two ILs were initially obtained using the solvent-evaporation method in mixed solvents. Single-crystal X-ray diffraction was used to determine the crystal structures.EAPy]PF6] crystallizes in the monoclinic space group C2/c with a=2.2748(16) nm, b=0.6204(4) nm, c=1.8552(12) nm and Z=8, whereasEAMPy]PF6] crystallizes in the orthorhombic space group P212121 with a=0.7126(17) nm, b=1.2792(3) nm, c=1.5327(3) nm and Z=4. The structure ofEAPy]PF6] contains double zigzag chains formed by alternately pairing large organic cations with the octahedral anions ofP1F6]- orP2F6]-. TheP1F6]- andP2F6]- anions occupy respectively two distinct crystallographic sites in crystal packing models. The structure ofEAMPy]PF6] includes ladder-type chains constructed through pairing pyridinium cations with inorganic anions ofPF6]-. ThePF6]- anion inEAMPy]PF6] shows a distorted octahedron structure and is sandwiched by ethyl acetate groups in crystallographic stacking. This study reveals the influence of chemical mo-dification involving the methyl group(CH3) onto crystallographic structure of pyridinium ILs. Thermal analysis indicates that the difficult crystallization of the two ILs is related to the low void filling of ion pairs in crystal structure, leading to relatively low melting point and evident supercooling during the cooling process. Additionally, the experimental results indicate that the two ILs have electrochemical activity. The ethyl acetate group also allows downward shifting of electrochemical windows to less negative positions and the ionic conductivities of the two ILs follow an Arrhenius-type behavior. |
| |
| Keywords: | Pyridinium ionic liquid Crystal structure Thermal analysis Electrochemical property |
|
| 点击此处可从《高等学校化学研究》浏览原始摘要信息 |
| 点击此处可从《高等学校化学研究》下载免费的PDF全文 |
|
