缩醛胺共价有机框架

doi:10.6023/cjoc202604053

摘要/Abstract

共价有机框架（COF）作为一类晶态有机多孔聚合物,凭借独特结构与性能在多个领域展现出广阔应用前景,而连接键是调控其性能、拓展其应用的关键位点。缩醛胺具有四面体构型和良好的反应可逆性,此前长期局限于有机合成领域。2019年缩醛胺键连COF（缩醛胺COF）首次被报道,填补了其在晶态多孔材料领域的空白,该类COF表现出独特的理化性质与应用潜力。然而,受成键方式特别、单体种类有限且结构匹配性要求高等因素制约,目前缩醛胺COF的研究十分匮乏,其发展与潜在应用价值不匹配。本文以缩醛胺COF的拓扑结构为分类依据,系统总结其结构特点、理化性质与应用领域,剖析研究现状与核心瓶颈,展望未来研究方向,为这一新类型COF的结构设计、性能优化及应用拓展提供参考,推动缩醛胺COF领域的发展。

关键词: 共价有机框架, 缩醛胺, 连接键, 四面体构型, 拓扑结构

Covalent organic frameworks (COFs) are crystalline organic porous polymers with promising applications in many fields owing to their distinctive structures and properties. Linkages serve as critical targets for modulating their physicochemical performance and expanding application scopes. Aminal linkages possess tetrahedral configuration and favorable reaction reversibility, which have been merely confined to organic synthesis for a long period. Aminal-linked COFs were first reported in 2019, which filled the research gap in crystalline porous materials. Such materials display unique physicochemical properties and tremendous functional potentials. Nevertheless, current studies on aminal-linked COFs are extremely scarce. Their development progress fails to match their potential application value, owing to unique bond formation, high requirement for structural matching, and limited monomers. Accordingly, on the basis of topological classifications, this review systematically summarizes the structural characteristics, physicochemical properties and application fields of aminal-linked COFs. We further analyze the current research status and major bottlenecks, and prospect future research directions. This work is expected to provide references for structural design, performance optimization and application extension, and promote the further development of aminal-linked COFs.

Key words: covalent organic frameworks (COFs), aminal, linkage, tetrahedral configuration, topological structure

引用此文

高泽昕, 王桢学, 王文壮, 齐巧艳, 梁荣冉, 赵新. 缩醛胺共价有机框架[J]. 有机化学, doi: 10.6023/cjoc202604053.

Gao Ze-Xin, Wang Zhen-Xue, Wang Wen-Zhuang, Qi Qiao-Yan, Liang Rong-Ran, Zhao Xin. Aminal-Linked Covalent Organic Frameworks[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202604053.

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参考文献

[1] Diercks C. S.; Yaghi O. M. Science2017, 355, 6328.
[2] Geng K.-Y.; He T.; Liu R.-Y.; Dalapati S.; Tan K.-T.; Li Z.-P.; Tao S.-S.; Gong Y.-F.; Jiang Q.-H.; Jiang D.-L. Chem. Rev.2020, 120, 8814.
[3] Arora N.; Flores C.; Senarathna M. C.; Thompson C. M.; Smaldone, R. A. CCS Chem.2024, 6, 57.
[4] Côté A. P.; Benin A. I.; Ockwig N. W.; O'Keeffe M.; Matzger A. J.; Yaghi O. M. Science2005, 310, 1166.
[5] Qian Y.-Y.; Jiang, H.-L. Acc. Chem. Res.2024, 57, 1214.
[6] Yusran Y.; Li H.; Guan X.-Y.; Fang Q.-R.; Qiu S.-L. EnergyChem2020, 2, 100035.
[7] Wang X.; Liu M.; Zhong Y.; Song, R. Chin. J. Org. Chem.2025, 45, 448 (in Chinese).
(王轩, 柳茂陈, 钟瑶, 宋仁杰, 有机化学, 2025, 45, 448).
[8] Song L.-L.; Zhang Q.; Min L.; Guo X.-Y.; Gao W.-Q.; Cui L.; Zhang C.-Y. Talanta2024, 266, 124964.
[9] Song L.-L.; Cui, L; Zou X.-R.; Cao X.-T.; Chu W.-Q.; Gao W.-J.; Cheng L.; Sun B.; Zhang, C.-Y. Chem. Eng. J.2025, 525, 170101.
[10] Yu G.; Wang, C. Chin. J. Org. Chem.2020, 40, 1437 (in Chinese).
(于歌, 汪成, 有机化学, 2020, 45, 1437).
[11] Sun J.-L.; Xu Y.-F.; Lv Y.-Q.; Zhang Q.-C.; Zhou X.-S. CCS Chem.2023, 5, 1259.
[12] Zhu L.-Y.; Cao Y.; Xu T.; Yang H.-B.; Wang L.-Y.; Dai L.; Pan F.-S.; Chen C.-J.; Si, C.-L. Energy Environ. Sci.2025, 18, 5675.
[13] Chafiq M.; Chaouiki A.; Ko, Y. G. Energy Storage Mater.2023, 63, 103014.
[14] Yin Y.; Zhang Y.; Zhou X.; Gui B.; Wang W.-Q.; Jiang W.-T.; Zhang Y.-B.; Sun J.-L.; Wang C. Science2024, 386, 693.
[15] Wang Z.-F.; Zhang S.-N.; Chen Y.; Zhang Z.-J.; Ma, S.-Q. Chem. Soc. Rev.2020, 49, 708.
[16] Wang J.-L.; Zhuang, S.-T. Coordin. Chem. Rev.2019, 400, 213046.
[17] Ge S.-B.; Wei K.-X.; Peng W.-X.; Huang R.-Z.; Akinlabi E.; Xia H.-Y.; Shahzad M. W.; Zhang X.-H.; Xu B.-B.; Jiang, J.-C. Chem. Soc. Rev.2024, 53, 11259.
[18] Ge, L.; Qiao, C.-Y.; Tang, Y.-K.; Zhang, X.-K.; Jiang, X.-Q.Nano Lett. 2021, 21, 3218.
[19] Mokhtari N.; Dinari M.; Esmaeiltarkhani, F. K. ACS Omega2023, 8, 25565.
[20] Jin E.; Asada M.; Xu Q.; Dalapati S.; Addicoat M. A.; Brady M. A.; Xu H.; Nakamura T.; Heine T.; Chen Q.; Jiang D. Science2017, 357, 673.
[21] Acharjya A.; Pachfule P.; Roeser J.; Schmitt F.-J.; Thomas, A. Angew. Chem. Int. Ed.2019, 58, 14865.
[22] Panda P.; Panda T. RSC Adv.2025, 15, 43013.
[23] Zhao W.; Wang X.-Y.; Bahri M.; Zhu Q.; Li B.-Y.; Wu K.; Wang Z.-K.; Li H.; Shi X.-S.; Shi D.-C.; Ji C.-Q.; Browning N. D.; Sun J.-G.; Wang J.-H.; Zhao, D. J. Am. Chem. Soc.2025, 147, 16319.
[24] Zhou Z.-B.; Han X.-H.; Qi Q.-Y.; Gan S.-X.; Ma D.-L.; Zhao, X. J. Am. Chem. Soc.2022, 144, 1138.
[25] Li Y.-Y.; Zhou Z.-P.; Hong Y.-X.; Dong X.; Yang Y.-H.; Liang Z.-H.; Sun J.-L.; Chen X.-D.; Liu W.; Zheng, Z.-K. Chin. J. Chem.2023, 41, 405.
[26] Grunenberg L.; Savasci G.; Terban M. W.; Duppel V.; Moudrakovski I.; Etter M.; Dinnebier R. E.; Ochsenfeld C.; Lotsch, B. V. J. Am. Chem. Soc.2021, 143, 3430.
[27] Zhang M.-C.; Li Y.; Yuan W.-L.; Guo X.-H.; Bai C.-Y.; Zou Y.-D.; Long H.-H.; Qi Y.; Li S.; Tao G.-H.; Xia C.-Q.; Ma, L.-J. Angew. Chem. Int. Ed.2021, 60, 12396.
[28] Zhou, Z.-B.; Tian, P.-J.; Yao, J.; Lu, Y.; Qi, Q.-Y.; Zhao, X.2[28] Zhou, Z.-B.; Tian, P.-J.; Yao, J.; Lu, Y.; Qi, Q.-Y.; Zhao, X.Nat. Commun. 2022, 13, 2180.
[29] Xiao J.-Z.; Zhao Z.-H.; Zhang N.-N.; Che H.-T.; Qiao X.; Zhang G.-Y.; Chu X.; Wang Y.; Dong H.; Zhang, F.-M. Chin. J. Catal.2025, 69, 219.
[30] Zhou W.-L.; Chen, Y. Chin. Chem. Lett.2023, 34, 108221.
[31] Jiang S.-Y.; Gan S.-X.; Zhang X.; Li H.; Qi Q.-Y.; Cui F.-Z.; Lu J.; Zhao, X. J. Am. Chem. Soc.2019, 141, 14981.
[32] Xiao Y.; Lu J.; Chen K.; Cao Y.; Gong C.; Ke, F.-S. Angew. Chem. Int. Ed.2024, 63, e202404738.
[33] Wang P.-L.; Ding S.-Y.; Zhang Z.-C.; Wang Z.-P.; Wang, W. J. Am. Chem. Soc.2019, 141, 18004.
[34] Li J.; Wang J.; Wu Z.; Tao S.; Jiang, D. Angew. Chem. Int. Ed.2021, 60, 12918.
[35] Wang K.-W.; Jia Z.-F.; Bai Y.; Wang X.; Hodgkiss S. E.; Chen L.-J.; Chong S.-Y.; Wang X.-Y.; Yang H.-F.; Xu Y.-J.; Feng F.; Ward J. W.; Cooper, A. I. J. Am. Chem. Soc.2020, 142, 11131.
[36] Hou Y.-H.; Zhou P.; Liu F.-Y.; Tong K.; Lu Y.-Y.; Li Z.; Liang J.-L.; Tong M.-P. Nat. Commun.2024, 15, 7350.
[37] Yang X.-B.; Xu Q.; W W.; Zeng, G.-F. Angew. Chem. Int. Ed.2025, 64, e202504355.
[38] Xu S.; Zhang, Q. Mater. Today Energy2021, 20, 100635.
[39] Zhao Y.-Y.; Han Y.; Yu, Y.-J. Chem. Eng. J.2024, 497, 154997.
[40] Cheng J.; Wu Y.-T.; Zhang W.; Zhang J.; Wang L.; Zhou M.; Fan F.-T.; Wu X.-J.; Xu H.-X. Adv. Mater.2024, 36, 2305313.
[41] Qi B.; Shen R.-C.; Ke Z.-Y.; Wang S.; Li Y.-J.; Zhang P.; Xu D.-F.; Li X. Rare Met.2025, 44, 9543.
[42] Liu H.-Y.; Chu J.; Yin Z.-L.; Cai X.; Zhuang L.; Deng H.-X. Chem2018, 4, 1696.
[43] Gomes R. F. A.; Afonso, C. A. M. J. Chem. Educ.2023, 100, 4728.
[44] Pereira J. G.; Antonio J. P. M.; Mendonca R.; Gomes R. F. A.; Afonso, C. A. M. Green Chem.2020, 22, 7484.
[45] Uribe-Romo F. J.; Hunt J. R.; Furukawa H.; Klöck C.; O’Keeffe M.; Yaghi, O. M. J. Am. Chem. Soc.2009, 131, 4570.
[46] Ding S.-Y.; Gao J.; Wang Q.; Zhang Y.; Song W.-G.; Su C.-Y.; Wang, W. J. Am. Chem. Soc.2011, 133, 19816.
[47] Carpenter, A. J.; Chadwick, D. J.Tetrahedron 1985, 41, 3803.
[48] Couture A.; Deniau E.; Grandclaudon P.; Hoarau, C. J. Org. Chem.1998, 63, 3128.
[49] Wang Y.-Y.; Wang J.-B.; Ding X.-Y.; Yu X.-J.; Zhao Y.-D.; Pan Z.-X.; Xu L.-W.; Cheng W.-C.; Ji M.; Yuan C.-M.; Wang T.; Zhou, B.-L. ACS Appl. Polym. Mater.2024, 6, 13764.
[50] Liu S.; Dong H.; Zhang R.-J.; Zhang W.; Sun X.-W.; Geng S.-C.; Wang K.; Ma L.-N.; Huang, Y.-D. New J. Chem.2022, 46, 8847.
[51] Ou H.; You Q.; Li J.; Liao G.; Xia H.; Wang D. RSC Adv.2016, 6, 98487.
[52] Laybourn A.; Dawson R.; Clowes R.; Iggo J. A.; Cooper A. I.; Khimyak Y. Z.; Adams, D. J. Polym. Chem.2012, 3, 533.
[53] Schwab M. G.; Fassbender B.; Spiess H. W.; Thomas A.; Feng X.; Muellen, K. J. Am. Chem. Soc.2009, 131, 7216.
[54] Wu M.-M.; Zhao Y.; Zhang H.-Y.; Zhu J.; Ma Y.-M.; Li C.-X.; Zhang Y.-M.; Chen Y.-S. Nano Res.2022, 15, 9779.
[55] Kang C.-J.; Zhang Z.-Q.; Usadi A. K.; Calabro D. C.; Baugh L. S.; Yu K.-X.; Wang Y.-X.; Zhao D. J. Am. Chem. Soc.2022, 144, 3192.
[56] Song L.-L.; Gao W.-Q.; Han Q.-R.; Huang Y.-P.; Cui L.; Zhang C.-Y. Chem. Commun.2022, 58, 10524.
[57] Song L.-L.; Gao W.-Q.; Wang S.-W.; Bi H.-Q.; Deng S.-Y.; Cui L.; Zhang, C.-Y. Sensor Actuat. B-Chem.2022, 373, 132751.
[58] Yuan M.-J.; Ma F.-Y.; Chen L.-X.; Li B.-Y.; Dai X.; Shu J.; He L.-W.; Chen J.-C.; Lin S.-J.; Xie G.-H.; Chai, Z.-F; Wang, S.-O. J. Am. Chem. Soc.2024, 146, 1250.
[59] Liu C.; Liu K.-H.; Wang C.-M.; Liu H.-Y.; Wang H.-L.; Su H.-M.; Li X.-Y.; Chen B.-L.; Jiang J.-Z. Nat. Commun.2020, 11, 1047.
[60] Zhang X.; Wasson M. C.; Shayan M.; Berdichevsky E. K.; Ricardo-Noordberg J.; Singh Z.; Papazyan E. K.; Castro A. J.; Marino P.; Ajoyan Z.; Chen Z.; Islamoglu T.; Howarth A. J.; Liu Y.; Majewski M. B.; Katz M. J.; Mondloch J. E.; Farha, O. K. Coordin. Chem. Rev.2021, 429, 213615.
[61] Meng Y.; Luo Y.; Shi J.-L.; Ding H.-M.; Lang X.-J.; Chen W.; Zheng A.-M.; Sun J.-L.; Wang, C. Angew. Chem. Int. Ed.2020, 59, 3624.
[62] Qian Y.; Li D.; Han Y.; Jiang, H.-L. J. Am. Chem. Soc.2020, 142, 20763.
[63] Wang Q.-Y.; Liu J.; Cao M.; Hu J.-H.; Pang R.; Wang S.; Asad M.; Wei Y.-L.; Zang, S.-Q. Angew. Chem. Int. Ed.2022, 61, e202207130.
[64] Liu M.-H.; Yang S.-A.; Yang X.-B.; Cui C.-X.; Liu G.-J.; Li X.-W.; He J.; Chen G.-Z.; Xu Q.; Zeng G.-F. Nat. Commun.2023, 14, 3800.
[65] Zhao X.; Pachfule P.; Thomas, A. Chem. Soc. Rev.2021, 50, 6871.
[66] Liu S.; Yang H.-B.; Su X.; Ding J.; Mao Q.; Huang Y.-Q.; Zhang T.; Liu, B. J. Energy Chem.2019, 36, 95.
[67] Duan J.-J.; Chen S.; Jaroniec M.; Qiao S.-Z. ACS Catal.2015, 5, 5207.
[68] Xie F.; Wang N.; Chen H.; Li M.; Li Y.; Leng L.; Qu W.; Yang J.; Yang Z.; Li, H. J. Mater. Chem. A2025, 13, 41653.
[69] Hack J.; Maeda N.; Meier, D. M. ACS Omega,2022, 7, 39520.
[70] Zhang Z.; Li Y.; Zhong Y.; Li P.; Zhu L.; Zheng Z.; Jia B.; David M.; Fu Y.; Yu H.; Ma T. Sci. Adv.2025, 11, eadw6592.
[71] Guo R.; Zha Z.-Y.; Wang J.-X.; Wang Z.; Guiver M. D.; Zhao S. Small2024, 20, 2308904.
[72] Xu, M.; Yang, T.-X.; Zha, Z.-Y.; Wang, Z.; Zhao, S.Chem. Mater. 2026, 38, 2420.
[73] Yun H.; Kang M.; Kang D. W.; Kim H.; Choe J. H.; Kim S. Y.; Hong C. S. Small2023, 19, 2303640.
[74] Yang J.-W.; Han X.-H.; Feng X. RSC Adv.2024, 14, 21151.
[75] Brzezinski M.; Tyszka-gumkowska A.; Gorski A.; Potrzebowski M. J.; Polczyk T.; Wegner W.; Gawinkowski S.; Ostapko, J. Angew. Chem. Int. Ed.2026, 65, e22521.