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★
收稿日期: 2023-04-26
网络出版日期: 2023-05-26
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★
Received date: 2023-04-26
Online published: 2023-05-26
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)
有机智能材料可在特定外界刺激下改变其性能, 因而在诸多领域具备应用前景, 其刺激响应性通常由分子尺度的结构变化引起. 以柱[5]芳烃分子骨架为基础, 将萘取代的吩噻嗪引入柱[5]芳烃中, 合成了一种新型的骨架功能化柱[5]芳烃(N-萘基-吩噻嗪基柱[5]芳烃6). 通过对溶剂挥发法生长得到的化合物6的单晶进行研究, 发现该晶体具备热刺激响应性质, 能够在加热后, 实现单晶到单晶(Single-Crystal-to-Single-Crystal, SCSC)的转变, 其分子构象及堆积方式均发生显著变化. 进一步地, 通过X射线单晶衍射和热重分析验证了溶剂离去诱导单晶中分子构象转变的过程. 此外, 还发现改变客体溶剂种类也可以用来调节所生长单晶中分子的构象及堆积方式. 该工作从分子层面研究和表征了热刺激晶体原位转变现象, 为刺激响应智能材料的理性构筑提供依据.
马长顺 , 金苇航 , 童非 , 顾睿锐 , 曲大辉 . 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★[J]. 化学学报, 2023 , 81(6) : 572 -576 . DOI: 10.6023/A23040169
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.
| [1] | Zheng, Y.; Jia, X.; Li, K.; Xu, J.; Bu, X. H. Adv. Energy Mater. 2021, 12, 2100324. |
| [2] | Zhang, J. P.; Liao, P. Q.; Zhou, H. L.; Lin, R. B.; Chen, X. M. Chem. Soc. Rev. 2014, 43, 5789. |
| [3] | Mohanrao, R.; Sureshan, K. M. Angew. Chem., Int. Ed. 2018, 57, 1243. |
| [4] | Krishnan, B. P.; Sureshan, K. M. J. Am. Chem. Soc. 2015, 137, 1692. |
| [5] | Fujimoto, A.; Fujinaga, N.; Nishimura, R.; Hatano, E.; Kono, L.; Nagai, A.; Sekine, A.; Hattori, Y.; Kojima, Y.; Yasuda, N.; Morimoto, M.; Yokojima, S.; Nakamura, S.; Feringa, B. L.; Uchida, K. Chem. Sci. 2020, 11, 12307. |
| [6] | Kitagawa, D.; Kawasaki, K.; Tanaka, R.; Kobatake, S. Chem. Mater. 2017, 29, 7524. |
| [7] | Karothu, D. P.; Weston, J.; Desta, I. T.; Naumov, P. J. Am. Chem. Soc. 2016, 138, 13298. |
| [8] | Mondal, A.; Bhattacharya, B.; Das, S.; Bhunia, S.; Chowdhury, R.; Dey, S.; Reddy, C. M. Angew. Chem., Int. Ed. 2020, 59, 10971. |
| [9] | Jin, M.; Sumitani, T.; Sato, H.; Seki, T.; Ito, H. J. Am. Chem. Soc. 2018, 140, 2875. |
| [10] | Mobin, S. M.; Srivastava, A. K.; Mathur, P.; Lahiri, G. K. Dalton Trans. 2010, 39, 1447. |
| [11] | Ma, F.; Sun, R.; Sun, A.-H.; Xiong, J.; Sun, H.-L.; Gao, S. Inorg. Chem. Front. 2020, 7, 930. |
| [12] | Rodriguez-Jimenez, S.; Feltham, H. L.; Brooker, S. Angew. Chem., Int. Ed. 2016, 55, 15067. |
| [13] | Liu, F.; Xu, Y.; Zhao, L.; Zhang, L.; Guo, W.; Wang, R.; Sun, D. J. Mater. Chem. A 2015, 3, 21545. |
| [14] | Saini, A. K.; Natarajan, K.; Mobin, S. M. Chem. Commun. 2017, 53, 9870. |
| [15] | Jie, K.; Zhou, Y.; Li, E.; Huang, F. Acc. Chem. Res. 2018, 51, 2064. |
| [16] | Shi, B.; Shangguan, L.; Wang, H.; Zhu, H.; Xing, H.; Liu, P.; Liu, Y.; Liu, J.; Huang, F. ACS Mater. Lett. 2019, 1, 111. |
| [17] | Ogoshi, T.; Sueto, R.; Yoshikoshi, K.; Sakata, Y.; Akine, S.; Yamagishi, T. A. Angew. Chem., Int. Ed. 2015, 54, 9849. |
| [18] | Lee, S.; Kim, D.; Park, I.-H.; Jung, O.-S. CrystEngComm 2021, 23, 40. |
| [19] | Li, Y.; Zhao, B.; Xue, J. P.; Xie, J.; Yao, Z. S.; Tao, J. Nat. Commun. 2021, 12, 6908. |
| [20] | Zhang, Z.; Lin, Y.; Jin, J.; Gong, L.; Peng, Y.; Song, Y.; Shen, N.; Wang, Z.; Du, K.; Huang, X. Angew. Chem., Int. Ed. 2021, 60, 23373. |
| [21] | Li, N. Y.; Liu, D.; Ren, Z. G.; Lollar, C.; Lang, J. P.; Zhou, H. C. Inorg. Chem. 2018, 57, 849. |
| [22] | Li, H.; Qu, D.-H. Sci. China Chem. 2015, 58, 916. |
| [23] | Han, C.; Zhang, Z.; Chi, X.; Zhang, M.; Yu, G.; Huang, F. Acta Chim. Sinica 2012, 70, 1775. (in Chinese) |
| [23] | (韩成友, 张子彬, 池小东, 张明明, 喻国灿, 黄飞鹤, 化学学报, 2012, 70, 1775.) |
| [24] | Wang, K.; Tian, X.; Jordan, J. H.; Velmurugan, K.; Wang, L.; Hu, X.-Y. Chin. Chem. Lett. 2022, 33, 89. |
| [25] | Fa, S.; Kakuta, T.; Yamagishi, T.-A.; Ogoshi, T. CCS Chem. 2019, 1, 50. |
| [26] | Behera, H.; Yang, L.; Hou, J. L. Chin. J. Chem. 2020, 38, 215. |
| [27] | Yi, J.; Chen, M.; Xue, S.; Tao, Z. Chin. J. Org. Chem. 2016, 36, 653. (in Chinese) |
| [27] | (易君明, 陈明华, 薛赛凤, 陶朱, 有机化学, 2016, 36, 653.) |
| [28] | Wu, M.; Yang, Y.; Xue, M. Acta Chim. Sinica 2022, 80, 1057. (in Chinese) |
| [28] | (吴明港, 杨勇, 薛敏, 化学学报, 2022, 80, 1057.) |
| [29] | Yue, S.; Zhou, Y.; Yao, Y.; Xue, M. Acta Chim. Sinica 2014, 72, 1053. (in Chinese) |
| [29] | (岳诗雨, 周玉娟, 姚勇, 薛敏, 化学学报, 2014, 72, 1053.) |
| [30] | Xiao, M.; Cheng, M.; Shi, F. Sci. Sin. Chim. 2017, 47, 40. (in Chinese) |
| [30] | (肖萌, 成梦娇, 石峰, 中国科学: 化学, 2017, 47, 40.) |
| [31] | Cheng, M.; Gong, W.; Lu, M.; Ma, J.; Lu, Z.; Li, H. Chin. J. Chem. 2022, 40, 925. |
| [32] | Liu, J.; Sun, X. W.; Huang, T. T.; Zhang, Y. M.; Yao, H.; Wei, T. B.; Lin, Q. Chin. J. Chem. 2021, 39, 3421. |
| [33] | Li, Y. W.; Fu, Y. H.; Hou, J. L. Chin. J. Chem. 2022, 40, 1293. |
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