Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (6): 572-576.DOI: 10.6023/A23040169 Previous Articles     Next Articles

Communication

一种可单晶到单晶(SCSC)转变的新型柱[5]芳烃的合成及性质研究

马长顺, 金苇航, 童非, 顾睿锐*(), 曲大辉*()   

  1. 华东理工大学化学与分子工程学院 上海 200237
  • 投稿日期:2023-04-26 发布日期:2023-05-25
  • 作者简介:
    庆祝《化学学报》创刊90周年.
  • 基金资助:
    国家自然科学基金(22105071); 国家自然科学基金(22025503); 国家自然科学基金(22205064); 国家自然科学基金(2220102004); 上海市科技重大专项(2018SHZDZX03); 中央高校基本科研经费; 高校学科人才引进计划(B16017); 上海市科学技术委员会(21JC1401700); 浙江大学上海高等研究院星空科学基金(SN-ZJU-SIAS-006); 上海扬帆计划(21YF1409200); 以及上海浦江计划(22PJ1402200)

Synthesis and Characterization of a Novel Pillar[5]arene That can Undergo Single-Crystal-to-Single-Crystal (SCSC) Transformation

Changshun Ma, Weihang Jin, Fei Tong, Ruirui Gu(), Dahui Qu()   

  1. School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237
  • Received:2023-04-26 Published:2023-05-25
  • Contact: *E-mail: guruirui@ecust.edu.cn; dahui_qu@ecust.edu.cn
  • About author:
    Dedicated to the 90th anniversary of Acta Chimica Sinica.
  • Supported by:
    National Natural Science Foundation of China(22105071); National Natural Science Foundation of China(22025503); National Natural Science Foundation of China(22205064); National Natural Science Foundation of China(2220102004); Shanghai Municipal Science and Technology Major Project(2018SHZDZX03); Fundamental Research Funds for the Central Universities; Program of Introducing Talents of Discipline to Universities(B16017); Science and Technology Commission of Shanghai Municipality(21JC1401700); Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study(SN-ZJU-SIAS-006); Shanghai Sailing Program(21YF1409200); Shanghai Pujiang Program(22PJ1402200)

Organic smart materials are able to change their properties in response to specific stimuli, being a type of materials that are potential to be applied in many fields. The stimuli-responsive abilities often arise from variations of structures at the molecular level. In this study, a new type of skeleton-functionalized pillar[5]arene (N-naphthyl-phenothiazinyl-pillar[5]- arene, 6) was successfully synthesized by incorporating a quinoline structure with a naphthalene substitution into the pillar[5]arene skeleton. First, compound 2 was obtained through two-step reactions, and was further reacted with 2-aminothiophenol through an amine/carbonyl condensation followed by substitution to yield a quinone-type thiazine structure of pillar[5]arene 3. Compound 3 was further reduced to a phenol-type structure, i.e. compound 4, by sodium borohydride. Compound 4 was further functionalized with 2-bromo-naphthalene through palladium-catalyzed Buchwald-Hartwig reaction to yield compound 5. In order to improve stability, the hydroxy group of compound 5 was converted to a methoxy group by injecting iodomethane into the acetone reaction solution of compound 5, resulting in compound 6. Structure of compound 6 was characterized by 1H NMR (nuclear magnetic resonance spectroscopy), 13C NMR, high-resolution mass spectra (HRMS), and X-ray single-crystal diffraction. The single crystal of this new pillar[5]arene was able to undergo a single-crystal-to-single-crystal (SCSC) conformational transformation under heating, accompanied by a change in stacking mode. Moreover, it is found that changing the guest molecule can adjust the molecular conformation in the grown single crystal. X-ray single-crystal diffraction and thermogravimetric analysis were used to verify this transformation process. This work studies the solvent-induced crystal conformation transition process from the molecular level, which provides an example for the rational construction of stimuli-responsive smart materials.

Key words: smart materials, pillararenes, phenothiazine, single-crystal-to-single-crystal, stimuli responsiveness