利用超分子策略构筑具有聚集诱导发光(AIE)功能的二苯乙烯型分子开关

doi:10.6023/cjoc202210020

摘要/Abstract

二苯乙烯型分子开关是构筑具有刺激响应行为的动力学体系的常用单元, 不同于常见的四苯基乙烯类化合物, 开发具有聚集诱导发光(AIE)功能二苯乙烯型分子开关是一大挑战. 利用柱[5]芳烃的超分子作用构筑了一类新型的具有AIE性质的二苯乙烯型分子开关, 该类分子开关具有优良的热稳定性, 酸催化下能够实现定量的Z→E转化. 光驱动的逆过程在光稳态(PSS)时的Z构型选择性达到87%, 柱[5]芳烃的引入没有影响母体的开关性能. 在混合溶剂[四氢呋喃(THF)-水]中, 由于柱[5]芳烃的超分子自组装作用, 形成了稳定的聚集体, 从而表现出母体分子不具备的AIE性能, 这种超分子策略为构筑AIE型分子开关提供了新的思路.

关键词: 分子开关, 二苯乙烯, 柱[5]芳烃, 聚集诱导发光

Stilbene derivatives have been widely used for the construction of molecular switches having stimulus-response properties. Unlike the well-known tetraphenyl ethylene derivatives that have aggregation-induced emission (AIE) properties, it is a challenge to develop a stilbene molecular switch with AIE function. In this paper, a new type of stilbene molecular switch with AIE function was constructed by the supramolecular interaction of pillar[5]arene. This type of molecular switch has excellent thermal stability, and quantitative Z→E conversion can be achieved under acid catalysis. The light-driving reverse process achieved 87% of Z-configuration selectivity in the photostable state (PSS). The introduction of pillar[5]arene did not affect the switching performance of the parent compound. In a mixed solvent [tetrahydrofuran (THF)-H₂O], a stable aggregate was formed due to the supramolecular self-assembly of pillar[5]arene, which showed the AIE performance that the parent stilbene derivative did not possess. This supramolecular strategy opens a new window for building AIE-type molecular switches.

Key words: molecular switch, stilbene, pillar[5]arene, aggregation-induced emission

引用此文

刘铃, 浩涛涛, 伍晚花, 杨成. 利用超分子策略构筑具有聚集诱导发光(AIE)功能的二苯乙烯型分子开关[J]. 有机化学, 2023, 43(6): 2189-2196.

Ling Liu, Taotao Hao, Wanhua Wu, Cheng Yang. Stilbene-Based Molecular Switches with Aggregation Induced Emission (AIE) Function Constructed by Supramolecular Strategy[J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 2189-2196.

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图/表 5

图1. 降冰片二烯稠合的二苯乙烯衍生物分子开关化合物的合成及核磁表征(1H NMR, CDCl3)

Figure 1. Synthesis and 1H NMR characterization of norbornadiene-fused stilbene-based molecular switches (a) Synthetic route of the molecular switches; (b) 1Z; (c) 1Z in the presence of 0.5 equiv. of TFA; (d) 1E

图2. (a) 1E和1Z的紫外-可见吸收光谱[2.5×10–5 mol/L, 二氯甲烷(DCM)]及用341 nm光照1E后紫外-可见光谱的变化; (b) 1Z和1E的对映异构体的圆二色测试(2.5×10–5 mol/L, DCM)

Figure 2. (a) UV-vis spectra of 1E and 1Z (2.5×10–5 mol/L, DCM) and the changes of 1E upon irradiation at 341 nm for different periods; (b) CD spectra of the enantiomeric of 1Z and 1E (2.5×10–5 mol/L, DCM)

图3. (a) 2Z (5×10–5 mol/L)在THF/H2O混合溶剂中的荧光光谱; (b) 2Z在385 nm处吸收强度随含水量的比值变化; (c) 1Z (5× 10–5 mol/L)在THF/H2O混合溶剂中的荧光光谱; (d) 1Z在425 nm处吸收强度随含水量的比值变化(嵌入图为1Z固态时在365 nm紫外灯照射下的成像); (e)可能的1Z自组装促进AIE活性的机理图

Figure 3. (a) Fluorescence spectra of 2Z (5×10–5 mol/L) in mixed solvents of THF/H2O; (b) plot of (I/I0) values of 2Z at 385 nm changes with the ratio of water content; (c) Fluorescence spectra of 1Z (5×10–5 mol/L) in mixed solvents of THF/H2O; (d) plot of (I/I0) values of 1Z at 425 nm changes with the ratio of water content (inset: a picture of 1Z in solid taken under 365 nm UV irradiation); (e) possible mechanism of 1Z self-assembly promoting AIE activity

图4. (a) 1Z (1×10–4 mol/L)在含水量90%的混合溶剂(THF/H2O)中用310 nm光照的随着光照时间变化的荧光光谱; (b)向1Z (1×10–4 mol/L, 氯仿)中加入不同体积的聚己内酯(平均分子量80000, 25 mg/mL氯仿)荧光光谱的变化(嵌入图片为200 mg聚己内酯、20 mg 1Z形成的凝胶在365 nm紫外灯照射下的成像)

Figure 4. (a) Photoluminescence spectra of 1Z (1×10–4 mol/L) in 90% aqueous solution (THF/H2O) upon irradiation at 310 nm for different periods; (b) Changes of fluorescence spectra of 1Z (1×10–4 mol/L, CHCl3) after adding different amounts of polycaprolactone (average molecular weight: 80000, 25 mg/mL chloroform) (inset: a picture of the gel composed of 200 mg polycaprolactone and 20 mg 1Z taken under 365 nm irradiation)

图式1. 乙氧基柱[5]修饰的苯乙烯基溴的合成路线

Scheme 1. Synthetic route of styryl bromide modified by ethoxy-pillar[5]arene

参考文献 36

[1]	Erbas-Cakmak, S.; Leigh, D. A.; McTernan, C. T.; Nuss-baumer, A. L. Chem. Rev. 2015, 115, 10081. doi: 10.1021/acs.chemrev.5b00146 pmid: 26346838
[2]	Irie, M.; Fukaminato, T.; Matsuda, K.; Kobatake, S. Chem. Rev. 2014, 114, 12174. doi: 10.1021/cr500249p
[3]	Villarón, D.; Wezenberg, S. J. Angew. Chem., Int. Ed. 2020, 59, 2.
[4]	Koumura, N.; Zijlstra, R. W. J.; Van Delden, R. A.; Harada, N.; Feringa, B. L. Nature 1999, 401, 152. doi: 10.1038/43646
[5]	Feringa, B. L. J. Org. Chem. 2007, 72, 6635. pmid: 17629332
[6]	Feringa, B. L. Angew. Chem., Int. Ed. 2017, 56, 11060. doi: 10.1002/anie.201702979
[7]	Serreli, V.; Lee, C. F.; Kay, E. R.; Leigh, D. A. Nature 2007, 445, 523. doi: 10.1038/nature05452
[8]	Waldeck, D. H. Chem. Rev. 1991, 91, 415. doi: 10.1021/cr00003a007
[9]	Noyce, D. S.; Hartter, D. R.; Miles, F. B. J. Am. Chem. Soc. 1968, 90, 4633. doi: 10.1021/ja01019a021
[10]	(a) Zhang, Q.-Q.; Lin, P.-P.; Yang, L.; Tan, D.-H.; Feng, S.-X.; Wang, H.; Li, Q. Chin. J. Org. Chem. 2020, 40, 3314. (in Chinese) doi: 10.6023/cjoc202005048
	(张其奇, 林鹏鹏, 杨羚, 谭东航, 冯嗣欣, 王洪根, 李清江, 有机化学, 2020, 40, 3314.) doi: 10.6023/cjoc202005048
	(b) Chen, H.-C.; Wu, Yi.; Yu, Y.; Wang, P. Chin. J. Org. Chem. 2022, 42, 742. (in Chinese) doi: 10.6023/cjoc202109045
	(陈宏超, 吴奕晨, 于洋, 王鹏, 有机化学, 2022, 42, 742.) doi: 10.6023/cjoc202109045
[11]	Lerch, M. M.; Hansen, M. J.; Velema, W. A.; Szymanski, W.; Feringa, B. L. Nat. Commun. 2016, 7, 12054. doi: 10.1038/ncomms12054
[12]	(a) Wang, L.; Li, Q. Chem. Soc. Rev., 2018, 47, 1044. doi: 10.1039/C7CS00630F
	(b) Weng, G.-H.; Zhu, B.; Ye, Y.; Li, S. Chin. J. Org. Chem. 2015, 35, 309. (in Chinese) doi: 10.6023/cjoc201409021
	(翁官欢, 朱彬, 叶杨, 李世军, 有机化学, 2015, 35, 309.) doi: 10.6023/cjoc201409021
[13]	(a) Luo, J. D.; Xie, Z. L.; Lam, J. W. Y.; Cheng, L.; Chen, H. Y.; Qiu, C. F.; Kwok, H. S.; Zhan, X. W.; Liu, Y. Q.; Zhu, D. B.; Tang, B. Z. Chem. Commun. 2001, 18, 1740. pmid: 26492387
	(b) Mei, J.; Leung, N. L. C.; Kwok, R. T. K.; Lam, J. W. Y.; Tang, B. Z. Chem. Rev. 2015, 115, 11718. doi: 10.1021/acs.chemrev.5b00263 pmid: 26492387
	(c) Yang, H.; Li, H.; Yue, L.; Chen, X.; Song, D.; Yang, X.; Sun, Y.; Zhou, G.; Wu, Z. J. Mater. Chem. C 2021, 9, 2334. doi: 10.1039/D0TC05527A pmid: 26492387
	(d) Zhao, J.; Feng, Z.; Zhong, D.; Yang, X.; Wu, Y.; Zhou, G.; Wu, Z. Chem. Mater. 2018, 30, 929. doi: 10.1021/acs.chemmater.7b04708 pmid: 26492387
	(e) Zhao, J.; Dang, F.; Feng, Z.; Liu, B.; Yang, X.; Wu, Y.; Zhou, G.; Wu, Z.; Wong, W.-Y. Chem. Commun., 2017, 53, 7581. doi: 10.1039/C7CC03251J pmid: 26492387
[14]	Wei, P.; Zhang, J.-X.; Zhao, Z.; Chen, Y.; He, X.; Chen, M.; Gong, J.; Sung, H.-H.; Williams, I. D.; Lam, J. W. Y.; Tang, B.-Z. J. Am. Chem. Soc. 2018, 140, 1966. doi: 10.1021/jacs.7b13364
[15]	(a) Yao, J.; Wu, W.; Liang, W.; Feng, Y.; Zhou, D.; Chruma, J. J.; Fukuhara, G.; Mori, T.; Inoue, Y.; Yang, C. Angew. Chem., Int. Ed. 2017, 56, 6869. doi: 10.1002/anie.201702542
	(b) Xiao, C.; Wu, W.; Liang, W.; Zhou, D.; Kanagaraj, K.; Cheng, G.; Su, D.; Zhong, Z.; Chruma, J. J.; Yang, C. Angew. Chem., Int. Ed. 2020, 132, 8171. doi: 10.1002/ange.v132.21
	(c) Yao, J.; Wu, W.; Xiao, C.; Su, D.; Zhong, Z.; Mori, T.; Yang, C. Nat. Commun. 2021, 12, 2600. doi: 10.1038/s41467-021-22880-z
	(d) Peng, C.; Liang, W.; Ji, J.; Fan, C.; Kanagaraj, K.; Wu, W.; Cheng, G.; Su, D.; Zhong, Z.; Yang, C. Chin. Chem. Lett., 2021, 32, 345. doi: 10.1016/j.cclet.2020.03.079
	(e) Yu, X.; Wu, W.; Zhou, D.; Su, D.; Zhong, Z.; Yang, C. CCS Chemistry 2021, 3, 1945.
	(f) Zhang, D.; Liang, W.; Yi, J.; Chen, J.; Lv, Y.; Zhao, T.; Xiao, C.; Xie, X.; Wu, W.; Yang, C. Sci. China Chem. 2022, 65, 1149. doi: 10.1007/s11426-022-1233-x
[16]	Hao, T.-T.; Yang, Y.-S.; Liang, W.-T.; Fan, C.-Y.; Wang, X.; Wu, W.-H.; Chen, X.-C.; Fu, H.-Y.; Chen, H.; Yang, C. Chem. Sci. 2021, 12, 2614. doi: 10.1039/D0SC05213B
[17]	Hao, T.-T.; Liang, H.-R.; Ou-Yang, Y.-H.; Yin, C.-Z.; Zheng, X.-L.; Yuan, M.-L.; Li, R.-X.; Fu, H.-Y.; Chen, H. J. Org. Chem. 2018, 83, 4441. doi: 10.1021/acs.joc.8b00150
[18]	(a) Tian, X.; Zuo, M.; Niu, P.; Wang, K.; Hu, X. Chin. J. Org. Chem. 2020, 40, 1823. (in Chinese) doi: 10.6023/cjoc202003066
	(田雪琪, 左旻瓒, 牛蓬勃, 王开亚, 胡晓玉, 有机化学, 2020, 40, 1823.) doi: 10.6023/cjoc202003066
	(b) Bian, S.; Ye, J.-H.; Fan, Z.; Zhang, W. C.; Wang, L. Y. Chin. J. Org. Chem. 2016, 36, 855. (in Chinese) doi: 10.6023/cjoc201510030
	(卞松, 叶家海, 樊政, 张文超, 王乐勇, 有机化学, 2016, 36, 855.) doi: 10.6023/cjoc201510030
[19]	(a) Zhang, H.; Liu, Z.; Xin, F.; Hao, A. Chin. J. Org. Chem. 2012, 32, 219. (in Chinese)
	(张华承, 刘召娜, 辛飞飞, 郝爱友, 有机化学, 2012, 32, 219.) doi: 10.6023/cjoc1107141
	(b) Wu, X.; Duan, Q.; Ni, M.; Hu, X.; Wang, L. Chin. J. Org. Chem. 2014, 34, 437. (in Chinese)
	(吴旋, 段群鹏, 倪梦飞, 胡晓玉, 王乐勇, 有机化学, 2014, 34, 437.) doi: 10.6023/cjoc201312018
	(c) Wang, Z.; Liu, Y. A.; Yang, H.; Hu, W.; Wen, K. Org. Lett. 2022, 24, 1822. doi: 10.1021/acs.orglett.2c00272
[20]	Petermayer, C.; Dube, H. Acc. Chem. Res. 2018, 51, 1153. doi: 10.1021/acs.accounts.7b00638
[21]	Goulet-Hanssens, A.; Utecht, M.; Mutruc, D.; Titov, E.; Schwarz, J.; Grubert, L.; Bleger, D.; Saalfrank, P.; Hecht, S. J. Am. Chem. Soc. 2017, 139, 335. doi: 10.1021/jacs.6b10822 pmid: 27997152
[22]	Fredrich, S.; Bonasera, A.; Valderrey, V.; Hecht, S. J. Am. Chem. Soc. 2018, 140, 6432. doi: 10.1021/jacs.8b02982
[23]	Konrad, D. B.; Savasci, G.; Allmendinger, L.; Trauner, D.; Ochsenfeld, C.; Ali, A. M. J. Am. Chem. Soc. 2020, 142, 6538. doi: 10.1021/jacs.9b10430 pmid: 32207943
[24]	Hnid, I.; Frath, D.; Lafolet, F.; Sun, X.; Lacroix, J. C. J. Am. Chem. Soc. 2020, 142, 7732. doi: 10.1021/jacs.0c01213
[25]	Yin, J.; Khalilov, A. N.; Muthupandi, P.; Ladd, R.; Birman, V. B. J. Am. Chem. Soc. 2020, 142, 60. doi: 10.1021/jacs.9b11160
[26]	Luo, Q.; Fan, Q.; Huang, W. Chin. J. Org. Chem. 2007, 27, 175. (in Chinese)
	(罗千福, 范曲立, 黄维, 有机化学, 2007, 27, 175.)
[27]	Feringa, B. L.; van Delden, R. A.; Koumura, N.; Geertsema, E. M. Chem. Rev. 2000, 100, 1789. pmid: 11777421
[28]	Wang, Y.; Li, Q. Adv. Mater. 2012, 24, 1926. doi: 10.1002/adma.201200241
[29]	Fa, S.; Mizobata, M.; Nagano, S.; Suetsugu, K.; Kakuta, T.; Yamagishi, T.; Ogoshi, T. ACS Nano 2021, 15, 16794. doi: 10.1021/acsnano.1c06975
[30]	Zhao, D.; Neubauer, T. M.; Feringa1, B. L. Nat. Commun. 2015, 6, 6652. doi: 10.1038/ncomms7652
[31]	Blanco, V.; Leigh, D. A.; Marcos, V. Chem. Soc. Rev. 2015, 44, 5341. doi: 10.1039/C5CS00096C
[32]	Ryabchun, A.; Li, Q.; Lancia, F.; Aprahamian, I.; Katsonis, N. J. Am. Chem. Soc. 2019, 141, 1196. doi: 10.1021/jacs.8b11558
[33]	Mei, J.; Hong, Y. N.; Lam, J. W. Y.; Qin, A. J.; Tang, Y. H.; Tang, B. Z. Adv. Mater. 2014, 26, 5429. doi: 10.1002/adma.201401356
[34]	Xia, D.; Wang, P.; Ji, X.; Khashab, N. M.; Sessler, J. L.; Huang, F. Chem. Rev. 2020, 120, 6070. doi: 10.1021/acs.chemrev.9b00839
[35]	Xu, M.; Li, N.; Zhao, Z.; Shi, Z.; S, J.; Chen, L. Eur. J. Med. Chem. 2019, 174, 265. doi: 10.1016/j.ejmech.2019.04.050
[36]	Chen, J.; Ni, H.; Meng, Z.; Wang, J.; Huang, X.; Dong, Y.; Sun, C.; Zhang, Y.; Cui, L.; Li, J.; Jia, X.; Meng, Q.; Li, C. Nat. Commun. 2019, 10, 3546. doi: 10.1038/s41467-019-11553-7