1,3,5,7,9-五吡唑心环烯的合成及配位自组装  

Synthesis and coordination self-assembly of 1,3,5,7,9-pentapyrazolylcorannulene

作　　者：张逸璐 姚春瑞 张前炎[1] 谢素原[1] ZHANG Yilu;YAO Chunrui;ZHANG Qianyan;XIE Suyuan(State Key Laboratory of Physical Chemistry of Solid Surfaces,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China)

机构地区：[1]厦门大学化学化工学院,固体表面物理化学国家重点实验室,福建厦门361005

出　　处：《厦门大学学报（自然科学版）》2024年第1期49-55,共7页Journal of Xiamen University：Natural Science

摘　　要：[目的]由于结构张力等因素,碗状心环烯分子通常难以与金属离子形成配位笼状超分子结构.为了构筑碗状心环烯分子的配位笼结构,在其分子边缘修饰上具有配位功能的基团,研究其与金属间的配位自组装行为.[方法]通过1,3,5,7,9-五氯心环烯与吡唑的亲核取代反应,合成1,3,5,7,9-五吡唑心环烯,通过高分辨质谱、核磁共振波谱对其分子结构进行表征,利用紫外-可见吸收光谱和荧光发射光谱研究其光学性质,并通过核磁滴定和高分辨质谱,探究1,3,5,7,9-五吡唑心环烯分别与富勒烯C_(60)和AgSO_(3)CF_(3)在液相中的超分子自组装行为.[结果]结构表征结果表明所合成的1,3,5,7,9-五吡唑心环烯具有C_(5)对称性,吡唑基团的引入扩展了π共轭体系导致其吸收波长红移,同时增强了其荧光性能.核磁滴定和高分辨质谱分析显示,在液相中,1,3,5,7,9-五吡唑心环烯与C_(60)仅发生弱的主客体自组装行为,而可与Ag^(+)发生配位形成M_(5)L_(2)分子笼状结构.[结论]本研究成功合成了C_(5)对称且含有5个配位位点的1,3,5,7,9-五吡唑心环烯,可在液相中与Ag^(+)发生配位自组装行为,可能形成了一种M_(5)L_(2)形式的配位笼状超分子结构.[Objective] Functional group modification is one of the important means to provide coordination sites for the self-assembly of corannulene.The self-assembled structures of corannulene derivatives have potential applications in catalysis,materials and biomedicine.In 2019,we reported on the synthesis and characterization of 1,3,5,7,9-pentapyrrolylcorannulene and decapyrrolylcorannulene.To obtain corannulene derivatives with coordination function,herein we synthesized the 1,3,5,7,9-pentapyrazolylcorannulene molecule by modifying the perimeter of corannulene with pyrazolyl groups and studied its supramolecular coordination self-assembly with C_(60) and AgSO_(3)CF_(3),respectively.[Methods] Pyrazolyl functional groups were successfully modified at the perimeter of corannulene by one step five-fold nucleophilic substitution reaction.The molecular structure of the modified corannulene derivatives was characterized by matrix-assisted laser desorption ionization time-of-flight mass spectrometry(MALDI-TOF-MS) and nuclear magnetic resonance(NMR) spectroscopy.The photophysical properties were studied using UV-Vis absorption spectrum and fluorescence emission spectrum.The supramolecular coordination self-assembly of 1,3,5,7,9-pentapyrazolylcorannulene with fullerene C_(60) or AgSO_(3)CF_(3) was investigated by means of NMR titration.[Results] Through a regioselective chlorination reaction,the synthon of 1,3,5,7,9-pentachloro corannulene with C_(5) symmetry was synthesized,and then the five chloro groups of the synthon were substituted by pyrazolyl groups to obtain 1,3,5,7,9-pentapyrazolylcorannulene(1).The structure of compound 1 was characterized by MS and NMR.The UV-Vis absorption spectrum shows that the longest absorption wavelength of 1,3,5,7,9-pentapyrazolylcorannulene is 323 nm.Compared with unmodified corannulene and pentaphenyl corannulene,compound 1 shows a significant redshift.The energy level difference between the highest occupied molecular orbital(HOMO) and the lowest unoccupied molecular orbital(LUMO) of compoun

关 键 词：心环烯 1 3 5 7 9-五吡唑心环烯 配位自组装 

分 类 号：O613.42[理学—无机化学] O613.71[理学—化学]