硫杂冠醚环化四硫富瓦烯有机凝胶因子的合成及其凝胶性质研究  

Synthesis of thiocrown ether cyclized tetrathiafulvalene organogelator and study on its gel properties

作　　者：闫佳佳 徐超 夏艳[1] 李东风[1] 侯瑞斌[1] YAN Jia-jia;XU Chao;XIA Yan;LI Dong-feng;HOU Rui-bin(College of Chemistry and Life Science,Changchun University of Technology,Changchun 130012,China)

机构地区：[1]长春工业大学化学与生命科学学院,吉林长春130012

出　　处：《分子科学学报》2022年第6期499-505,共7页Journal of Molecular Science

基　　金：国家自然科学基金应急项目(21442004)。

摘　　要：在亚磷酸三乙酯存在下,中间体进行交叉偶联反应,成功合成了结构新颖的基于硫杂冠醚环化四硫富瓦烯(TTF)的低相对分子质量有机凝胶因子.采用NMR,MALDI-TOF-MS和IR对其分子结构进行充分表征.成胶能力实验表明该凝胶因子只能在DMSO溶剂中经超声处理形成不透明凝胶.用扫描电镜(SEM)对干凝胶的形貌进行观察,显示为具有微米尺寸的花状结构.此外,形成的凝胶对各种外部刺激表现出多种刺激响应,包括温度、氧化、阴离子和Na+.The synthetic crown ether has a unique position and plays an important role in the establishment and rapid development of supramolecular chemistry. Novel and functional crown ether derivatives are molecular recognition and sensing, molecular self-assembly, and the construction of multi-level and exquisite supramolecular nano-assemblies as molecular units and objects to construct optoelectronic functional systems, molecular machines and advanced materials. In recent years, small molecular gelling factors based on functional crown ether groups have become one of the research hotspots in supramolecular chemistry. Because crown ethers can form supramolecular gel systems through host-guest recognition and assembly, they have been applied in many fields, and their multiple stimulus responsiveness, shape persistence and elastic properties have been studied systematically.Crown ether gelators with redox activity are of particular interest because their affinity for different guests is reflected by the redox characteristics of the receptor, allowing the construction of supramolecular systems capable of controlled recognition and release of the subject. Tetrathiafulvalene(TTF) unit has excellent redox activity and has been widely used in the construction of supramolecular systems with electrical, optical and magnetic properties. In particular, low molecular weight organogel factors based on TTF units have been widely studied for the development of conductive nanomaterials, multiple stimulus responsive materials, etc.Herein we combined the thiocrown ether containing TTF moiety with alkyl-substituted amides. In the presence of triethyl phosphite, intermediates underwent a cross-coupling reaction to successfully form a novel low molecular weight organogelator based on thiocrown ether with TTF. Its molecular structure was fully characterized by NMR, MALDI-TOF-MS and IR, respectively. It was showed that the gelator could only form an opaque gel after ultrasonic treatment in DMSO solvent. The morphology of the dry gel was observ

关 键 词：四硫富瓦烯 硫杂冠醚 凝胶因子 多种刺激响应 

分 类 号：O626[理学—有机化学]