卤键驱动超分子自组装：从维度调控到功能应用

doi:10.6023/cjoc202605016

摘要/Abstract

卤键是一类由卤原子σ-空穴与亲核体之间形成的定向非共价相互作用。经典卤键源于电中性卤素原子（I、Br、Cl）与吸电子取代基共价连接后沿键轴方向产生的σ-空穴,具有方向性强和键能可调的特点,适于构筑开放型、可扩展的超分子网络。阳离子卤键则由卤鎓离子（X⁺）通过其p轨道空穴同时与两个路易斯碱配位,形成三中心四电子的[D···X···D]⁺特征单元,键能可达180 kJ·mol^-1,兼具共价性与静电性,展现出卓越的热力学稳定性和双齿桥连能力。基于上述差异,本文系统综述了两类卤键在超分子自组装中的结构构筑逻辑与维度调控策略,从零维到三维依次涵盖二聚体、胶囊、螺旋聚合物、二维卤键有机框架（XOFs）及三维晶体架构,重点分析了各维度下经典卤键的“单齿线性连接”与阳离子卤键的“双齿桥连节点”对组装拓扑和稳定性的不同贡献。进一步,总结了两类卤键驱动组装体在光催化、气体分离、医药等领域的功能应用。两类卤键在方向性、强度与组装行为上的互补特征,为晶体工程与功能材料设计提供了丰富的设计空间。

关键词: 卤键, 超分子自组装, 非共价相互作用, 晶体工程, 卤键有机框架

Halogen bonding is a class of directional noncovalent interactions formed between the σ-hole of a halogen atom and a nucleophile. Classical halogen bonding originates from the σ-hole generated along the bond axis of an electroneutral halogen atom (I, Br, Cl) covalently linked to an electron-withdrawing substituent, and is characterized by high directionality and tunable bond energies, making it suitable for the construction of open and expandable supramolecular networks. Cationic halogen bonding, in contrast, involves a halonium ion (X⁺) coordinating simultaneously with two Lewis bases through its p-orbital vacancy, giving rise to the characteristic three-center four-electron [D···X···D]⁺ motif, with bond energies reaching up to 180 kJ·mol^-1. This interaction exhibits both covalent and electrostatic character, endowing it with exceptional thermodynamic stability and bidentate bridging capability. On the basis of these distinctions, this review systematically surveys the structural construction logic and dimensionality control strategies of both types of halogen-bonded systems in supramolecular self-assembly, covering zero-dimensional to three-dimensional architectures including dimers, capsules, helical polymers, two-dimensional halogen-bonded organic frameworks (XOFs), and three-dimensional crystalline frameworks, with emphasis on the distinct contributions of the "monodentate linear connectivity" of classical halogen bonds and the "bidentate bridging nodes" of cationic halogen bonds to assembly topology and stability. Furthermore, the functional applications of these halogen-bonded assemblies in photocatalysis, gas separation, and biomedicine are summarized. The complementary features of classical and cationic halogen bonds in terms of directionality, bond strength, and assembly behavior provide a rich design space for crystal engineering and functional materials.

Key words: Halogen bond, Supramolecular self-assembly, Noncovalent interaction, Crystal engineering, Halogen-bonded organic framework

引用此文

张鹛媚, 王璐, 陈世贵. 卤键驱动超分子自组装：从维度调控到功能应用[J]. 有机化学, doi: 10.6023/cjoc202605016.

Meimei Zhang, lu Wang, Shigui Chen. Halogen Bonding Driven Supramolecular Self-Assembly: From Dimensionality Control to Functional Applications[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202605016.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] (a)Li, Y.; Zhao, C.; Wang, Z.; Zeng, Y. J. Phys. Chem. A 2024, 128, 507;
(b)Neaton, J. B. Sci. 2017, 358, 167;
(c)李芬; 刘传志; 户志远; 罗盼盼; 崔蓉铮; 黄彦珂; 刘新明; 刘澜涛; 吴玮有机化学 2023, 43, 705;
(d)Kaasik, M.; Kanger, T. Front. Chem. 2020, 8, 2296;
(e)Koivuporras, A.; Mailman, A.; Guo, H.; Priimagi, A.; Puttreddy, R. Cryst. Growth Des. 2023, 23, 8889;
(f)许艳艳; 刘传志; 王辉; 张丹维; 黎占亭有机化学 2021, 41, 2848;
(g)Sun, J.; Decato, D. A.; Bryantsev, V. S.; John, E. A.; Berryman, O. B. Chem. Sci. 2023, 14, 8924;
(h)Lu, J.; Scheiner, S. Comput. Theor. Chem. 2021, 1204, 113398;
(i)Gong, G.; Zhao, J.; Chen, Y.; Xie, F.; Lu, F.; Wang, J.; Wang, L.; Chen, S. J. Mater. Chem. A 2022, 10, 10586;
(j)田震南; 赵佳豪; 巩冠斐; 白旭冠; 李浩虎; 王纪科; 王璐; 蔡强; 陈世贵中国科学:化学 2023, 53, 2367;
(k)蒋志武; 袁振东化学通报 2023, 86, 761;
(l)Cavallo, G.; Metrangolo, P.; Milani, R.; Pilati, T.; Priimagi, A.; Resnati, G.; Terraneo, G. Chem. Rev. 2016, 116, 2478;
(m)Jovanovic, D.; Poliyodath Mohanan, M.; Huber, S. M. Angew. Chem. Int. Ed. 2024, 63, e202404823.
[2] Guthrie, F. J. Chem. Soc.1863, 16, 239.
[3] (a)Etter, M. C. [J]. Phys. Chem. 1991, 95, 4601
(b)刘传志; 李芬; 王静静; 赵晓璐; 张婷美; 黄鑫; 邬梦丽; 户志远; 刘新明; 黎占亭化学学报 2022, 80, 1365;
(c)Chuanzhi Liu, F. L., Jingjing Wang, Xiaolu Zhao, Tingmei Zhang, Xin Huang, Mengli Wu, Zhiyuan Hu, Xinming Liu, Zhanting Li Acta Chim. Sin. 2022, 80, 1365.
[4] (a)Desiraju, G. R.; Ho, P. S.; Kloo, L.; Legon, A. C.; Marquardt, R.; Metrangolo, P.; Politzer, P.; Resnati, G.; Rissanen, K. 2013, 85, 1711
(b)Mukherjee, A.; Tothadi, S.; Desiraju, G. R. Acc. Chem. Res. 2014, 47, 2514.
[5] (a)Huber, S. M.; Walter, S. M.; Kniep, F.; Herdtweck, E.; Rout, L.; Bensch, H. K. V.; Jungbauer, S. H. Abstr. Pap. Am. Chem. Soc. 2013, 245, 10350;
(b)Carlsson, A. C. C.; Gräfenstein, J.; Laurila, J. L.; Bergquist, J.; Erdélyi, M. Chem. Commun. 2012, 48, 1458
(c)Carlsson, A.-C. C.; Gräfenstein, J.; Budnjo, A.; Laurila, J. L.; Bergquist, J.; Karim, A.; Kleinmaier, R.; Brath, U.; Erdélyi, M. J. Am. Chem. Soc. 2012, 134, 5706;
(d)Ding, X. H.; Chang, Y. Z.; Ou, C. J.; Lin, J. Y.; Xie, L. H.; Huang, W. Natl. Sci. Rev. 2020, 7, 1906.
[6] (a)Nguyen, H. L.; Horton, P. N.; Hursthouse, M. B.; Legon, A. C.; Bruce, D. W. J. Am. Chem. Soc. 2004, 126, 16;
(b)Carter, M.; Ho, P. S. Cryst. Growth Des. 2011, 11, 5087
(c)Tepper, R.; Schubert, U. S. Angew. Chem. Int. Ed. 2018, 57, 6004;
(d)Zhu, Z.; Xu, Z.; Zhu, W. J. Chem. Inf. Model. 2020, 60, 2683;
(e)Metrangolo, P.; Resnati, G.; Pilati, T.; Liantonio, R.; Meyer, F. J. Polym. Sci. Pol. Chem. 2007, 45, 1;
(f)Dong, W.; Zhang, Y.; Yi, C.; Chang, J. J.; Ye, S.; Nie, Z. ACS Nano 2023, 17, 3047;
(g)Liu, C. Z.; Koppireddi, S.; Wang, H.; Zhang, D. W.; Li, Z.-T. Chin. Chem. Lett. 2019, 30, 953;
(h)Bulfield, D.; Engelage, E.; Mancheski, L.; Stoesser, J.; Huber, S. M. Chemistry-A European Journal 2020, 26, 1567.
[7] (a)Bedin, M.; Karim, A.; Reitti, M.; Carlsson, A. C. C.; Topic, F.; Cetina, M.; Pan, F. F.; Havel, V.; Al-Ameri, F.; Sindelar, V.; Rissanen, K.; Gräfenstein, J.; Erdélyi, M. Chem. Sci. 2015, 6, 3746
(b)Karim, A.; Reitti, M.; Carlsson, A. C. C.; Gräfenstein, J.; Erdélyi, M. Chem. Sci. 2014, 5, 3226;
(c)Wang, H.; Wang, W.; Jin, W. J. Chem. Rev. 2016, 116, 5072;
(d)Maji, S.; Natarajan, R. Small 2023, 19;
(e)Lindblad, S.; Mehmeti, K.; Veiga, A. X.; Nekoueishahraki, B.; Gräfenstein, J.; Erdélyi, M. J. Am. Chem. Soc. 2018, 140, 13503;
(f)Turunen, L.; Erdélyi, M. Chem. Soc. Rev. 2020, 49, 2688.
[8] (a)Clark, T.; Hennemann, M.; Murray, J. S.; Politzer, P. J. Mol. Model. 2007, 13, 291;
(b)Wu, Q.; Li, Y. J.; Jiang, Q. Q.; Wang, Y. A.; Zhang, R.; Luo, Q. X.; Ke, H.; Liang, R. P.; Qiu, J. D. Sep. Purif. Technol. 2024, 338.
[9] (a)Politzer, P.; Murray, J. S.; Clark, T. Phys. Chem. Chem. Phys. 2013, 15, 11178;
(b)Hassel, O. Sci. 1970, 170, 497.
[10] (a)Reiersølmoen, A. C.; Battaglia, S.; Øien-Ødegaard, S.; Gupta, A. K.; Fiksdahl, A.; Lindh, R.; Erdélyi, M. Chem. Sci. 2020, 11, 7979
(b)Hakkert, S. B.; Erdélyi, M. [J]. Phys. Org. Chem. 2015, 28, 226.
[11] (a)Carlsson, A. C. C.; Mehmeti, K.; Uhrbom, M.; Karim, A.; Bedin, M.; Puttreddy, R.; Kleinmaier, R.; Neverov, A. A.; Nekoueishahraki, B.; Gräfenstein, J.; Rissanen, K.; Erdélyi, M. [J]. Am. Chem. Soc. 2016, 138, 9853
(b)Wang, S.; Dong, H.; Gong, G.; Lin, S.; Zhao, J.; Tian, Z.; Lu, Y.; Bai, X.; Zhang, M.; Wang, L.; Zhang, K.-D.; Chen, S. Mater. Chem. Front. 2024, 8, 4096;
(c)Zhao, Q.; Sun, P.; Gong, G.; Chen, Y.; Luo, L.; Yin, Y.; Li, C.; Wang, J.; Wang, L.; Chen, S. Sci. China Chem. 2025, 68, 631;
(d)Xia, N.; Han, J.; Xie, F.; Gong, G.; Wang, L.; Wang, J.; Chen, S. ACS Appl. Mater. Interfaces 2022, 14, 43621.
[12] Erdélyi, M. Chem. Soc. Rev. 2012, 41, 3547.
[13] (a)Michalczyk, M. ChemPhysChem 2025, 26, e202500357;
(b)Fanfrlík, J.; Ruiz, F. X.; Kadlčíková, A.; Řezáč, J.; Cousido-Siah, A.; Mitschler, A.; Haldar, S.; Lepšík, M.; Kolář, M. H.; Majer, P.; Podjarny, A. D.; Hobza, P. ACS Chem. Biol. 2015, 10, 1637.
[14] Bhattarai S.; Sutradhar D.; Chandra A. K.[J]. Mol. Struct. 2021, 1223, 129239.
[15] Raffo P. A.; Marcolongo J. P.; Funes A. V.; Slep L. D.; Baggio R. F.; Cukiernik F. D.[J]. Mol. Struct. 2016, 1108, 235.
[16] Devore D. P.; Ellington T. L.; Shuford K. L. ChemPhysChem 2024, 25, e202400607.
[17] Zhang M.; Bai X.; Tian Z.; Zhao J.; Wang J.; Wang L.; Chen S. Chem. Eur. J. 2026, 32, e70683.
[18] (a)Gholipour, A.; Farhadi, S.; Neyband, R. S. Struct. Chem. 2016, 27, 1543
(b)Bowling, N. P.; Speetzen, E. D.; Bosch, E. ChemPlusChem 2021, 86, 745.
[19] Decato D. A.; Sun J.; Boller M. R.; Berryman O. B. Chem. Sci. 2022, 13, 11156.
[20] Teng P.; Gray G. M.; Zheng M.; Singh S.; Li X.; Wojtas L.; van der Vaart, A.; Cai, [J]. Angew. Chem. Int. Ed. 2019, 58, 7778.
[21] Vanderkooy A.; Gupta A. K.; Földes T.; Lindblad S.; Orthaber A.; Pápai I.; Erdélyi, M. Angew. Chem. Int. Ed. 2019, 58, 9012.
[22] (a)Lindblad, S.; Németh, F. B.; Földes, T.; von der Heiden, D.; Vang, H. G.; Driscoll, Z. L.; Gonnering, E. R.; Pápai, I.; Bowling, N.; Erdelyi, M. Chem. Eur. J. 2021, 27, 13748;
(b)Wang, S.; Tian, Z.; Gong, G.; Zhao, J.; Dong, H.; Bai, X.; Wang, L.; Chen, S. Chin. J. Chem. 2025, 43, 1824
(c)Zhao, J.; Xia, N.; Dong, H.; Ding, X.; Gong, G.; Wang, S.; Bai, X.; Tian, Z.; Zhang, M.; Wang, J.; Wang, L.; Chen, S. Chem. Eng. J. 2025, 512, 162529;
(d)Zhao, Q.; Lin, S.; Sun, P.; Lu, Y.; Li, Q.; Tian, Z.; Bai, X.; Wang, J.; Wang, L.; Chen, S. Adv. Funct. Mater. 2025, 35, 2421755;
(e)Dong, H.; Yu, S.; Wang, S.; Zhao, J.; Bai, X.; Lei, S.; Tian, Z.; Tian, J.; Zhang, K.; Wang, L.; Li, Z.; Chen, S. Chin. Chem. Lett. 2025, 36, 110730;
(f)Ding, X.; Zhao, J.; Tian, Z.; Li, Q.; Dong, H.; Zhang, M.; Wang, L.; Chen, S. Chin. J. Chem. 2026, 44, 2013.
[23] (a)Torita, K.; Haraguchi, R.; Morita, Y.; Kemmochi, S.; Komatsu, T.; Fukuzawa, S.-i. Chem. Commun. 2020, 56, 9715
(b)Wang, S.; Lu, Y.; Dong, H.; Tian, Z.; Zhao, J.; Gong, G.; Wang, L.; Chen, S. Tetrahedron 2026, 196, 135287.
[24] (a)Turunen, L.; Warzok, U.; Puttreddy, R.; Beyeh, N. K.; Schalley, C. A.; Rissanen, K. Angew. Chem. Int. Ed. 2016, 55, 14033;
(b)Turunen, L.; Peuronen, A.; Forsblom, S.; Kalenius, E.; Lahtinen, M.; Rissanen, K. Chem. Eur. J. 2017, 23, 11714;
(c)Turunen, L. Chem 2017, 3, 715.
[25] Szell P. M.J.; Cavallo, G.; Terraneo, G.; Metrangolo, P.; Gabidullin, B.; Bryce, D. L. Chem. Eur. J. 2018, 24, 11364.
[26] An S.; Hao A.; Xing P. Chem.Sci. 2023, 14, 10194.
[27] Beyeh N. K.; Pan F.; Rissanen K. Angew. Chem. Int. Ed. 2015, 127, 7411.
[28] Warzok U.; Marianski M.; Hoffmann W.; Turunen L.; Rissanen K.; Pagel K.; Schalley C. A. Chem. Sci. 2018, 9, 8343.
[29] Liu C.-Z.; Koppireddi S.; Wang H.; Zhang D.-W.; Li, Z.-T. Angew. Chem. Int.Ed. 2019, 58, 226.
[30] Bosch E.; Bowling N. P. Cryst. Growth Des. 2019, 19, 5929.
[31] An S.; Hao A.; ReferencesXing, P. ACS Nano 2022, 16, 19220.
[32] Radzhabov A. D.; Ledneva A. I.; Soldatova N. S.; Fedorova I. I.; Ivanov D. M.; Ivanov A. A.; Yusubov M. S.; Kukushkin V. Y.; Postnikov P. S. Int. J. Mol.Sci. 2023, 24, 14642.
[33] Soldatova N. S.; Knyazeva E. V.; Kukushkin V. Y.; Postnikov P. S. Coord. Chem. Rev. 2026, 556, 217585.
[34] (a)Gong, G.; Lv, S.; Han, J.; Xie, F.; Li, Q.; Xia, N.; Zeng, W.; Chen, Y.; Wang, L.; Wang, J.; Chen, S. Angew. Chem. Int. Ed. 2021, 60, 14831;
(b)Zhao, J.; Xia, N.; Tian, Z.; Xie, F.; Dong, H.; Gong, G.; Bai, X.; Wang, J.; Wang, L.; Chen, S. ACS Mater. Lett. 2024, 6, 508;
(c)Bai, X.; Tian, Z.; Dong, H.; Xia, N.; Zhao, J.; Sun, P.; Gong, G.; Wang, J.; Wang, L.; Li, H.; Chen, S. Angew. Chem. Int. Ed. 2024, 63, e202408428;
(d)Bai, X.; Tian, Z.; Dong, H.; Zhao, J.; Qi, Q.; Lei, S.; Sun, M.; Wei, M.; Zeng, J.; He, S.; Tian, J.; Wang, L.; Wang, J.; Li, H.; Chen, S. CCS Chem. 2026, 8, 2583.
[35] Gümüşgöz Çelik, G.; Dedeoglu, B.; Gürek, A. G.; Zorlu, Y.; Ayhan, M. M. Cryst. Growth Des. 2023, 23, 7285.
[36] Soldatova N. S.; Postnikov P. S.; Ivanov D. M.; Semyonov O. V.; Kukurina O. S.; Guselnikova O.; Yamauchi Y.; Wirth T.; Zhdankin V. V.; Yusubov M. S.; Gomila R. M.; Frontera A.; Resnati G.; Kukushkin V. Y. Chem. Sci. 2022, 13, 5650.
[37] (a)Zhao, J.; Xia, N.; Dong, H.; Lu, Y.; Tian, Z.; Ding, X.; Bai, X.; Wang, L.; Chen, S. Sci. China Chem. 2026, 69, 1375
(b)Dong, H.; Zhao, J.; Lu, Y.; Tian, Z.; Wang, S.; Bai, X.; Gong, G.; Wang, J.; Wang, L.; Chen, S. [J]. Energy Chem. 2025, 108, 527.
[38] Yang T.; Jiang X.; Sun X.; Dong Y.; Zhu Y. Appl. Catal. B Environ. 2026, 389, 126572.
[39] Bai X.; Liao H.; Zhao J.; Dong H.; Tian Z.; Lu Y.; Lei S.; Tian J.; Wang J.; Wang L.; Chen S. Adv. Funct. Mater. 2026, 36, e27110.
[40] Sun P.; Dong H.; Lv S.; Yin Y.; Gong G.; Wang L.; Wang J.; Chen S. J. Mater. Chem. A 2024, 12, 1128.
[41] Jia Q.; Zhao C.; Zhu W.; Fang N.; He X.; Zhao Y. Angew. Chem. Int. Ed. 2025, 64, e202517907.
[42] Tian Z.; Zhou S.; Qu Y.; Yang Q.; Bai X.; Zhao J.; Dong H.; Lu Y.; Deng N.; Wang L.; Pi L.; Cheng Y.; Chen S.; Liu W. Aggregate 2025, 6, e70050.
[43] Lin S.; Xu Q.; Bai X.; Tian Z.; Wang L.; Han F.; Chen S.; Cai Q. Chin. Chem. Lett. 2026, 37, 111425.