文献类型：期刊文献

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

作者：Ma Changshun[1];Jin Weihang[1];Tong Fei[1];Gu Ruirui[1];Qu Dahui[1]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China

年份：2023

卷号：81

期号：6

起止页码：572

外文期刊名：ACTA CHIMICA SINICA

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001028856300003)】；

基金：Project supported by the National Natural Science Foundation of China (Nos. 22105071, 22025503, 22205064, 2220102004), the Shanghai Municipal Science and Technology Major Project (No. 2018SHZDZX03), the Fundamental Research Funds for the Central Universities, the Program of Introducing Talents of Discipline to Universities (No. B16017), the Science and Technology Commission of Shanghai Municipality (No. 21JC1401700), the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study (No. SN-ZJU-SIAS-006), the Shanghai Sailing Program (No. 21YF1409200), and the Shanghai Pujiang Program (No. 22PJ1402200).

语种：英文

外文关键词：smart materials; pillararenes; phenothiazine; single-crystal-to-single-crystal; stimuli responsiveness

摘要：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 H-1 NMR (nuclear magnetic resonance spectroscopy), C-13 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.