Recent Advances in Metal–Macrocycle-BasedSupramolecular Polymers and Their Assemblies
DOI:
https://doi.org/10.62177/jaet.v3i3.1614Keywords:
Metal–Organic Macrocycles, Supramolecular Polymers, Hierarchical Self-Assembly, Coordination-Driven Assembly, Stimuli-Responsive MaterialsAbstract
Metal–macrocycle-based supramolecular polymers represent a frontier in smart materials, seamlessly integrating the highly tunable architectures of metal–organic macrocycles with the dynamic properties of hierarchical assemblies. This Review comprehensively evaluates recent advances in the coordination-driven synthesis and self-assembly of these tailored materials. By employing specific transition metal nodes (e.g., Pt, Pd, Fe), researchers can precisely engineer macrocyclic topologies while embedding intrinsic photophysical, electrochemical, and catalytic functionalities. We systematically analyze how secondary noncovalent interactions—such as host–guest recognition and hydrogen bonding—propel the hierarchical assembly of these building blocks from discrete molecular entities to macroscopic functional materials. Furthermore, we highlight how the dynamic nature of coordination bonds endows these assemblies with remarkable stimuli-responsiveness and self-adaptive capabilities. Finally, we discuss cutting-edge applications in biomedicine, smart sensing, and heterogeneous catalysis, alongside a critical perspective on the current bottlenecks and future directions necessary for translating these bespoke supramolecular systems into practical technologies.
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References
Harada, A., Hashidzume, A., Yamaguchi, H., & Takashima, Y. (2009). Polymeric Rotaxanes. Chemical Reviews, 109(11), 5974~6023. https://doi.org/10.1021/cr9000622
Wang, H., Ji, X., Li, Z., & Huang, F. (2017). Fluorescent Supramolecular Polymeric Materials. Advanced Materials, 29(14), 1606117. https://doi.org/10.1002/adma.201606117
Zhang, J., Qiu, H., He, T., Li, Y., & Yin, S. (2020). Fluorescent Supramolecular Polymers Formed by Crown Ether-Based Host-Guest Interaction. Frontiers in Chemistry, 8, 560. https://doi.org/10.3389/fchem.2020.00560
Zhao, Y., Zheng, Z., Yu, C.-Y., & Wei, H. (2024). Engineered cyclodextrin-based supramolecular hydrogels for biomedical applications. Journal of Materials Chemistry B, 12(1), 39~63. https://doi.org/10.1039/D3TB02101G
Wang, L., Song, B., Khalife, S., Li, Y., Ming, L.-J., Bai, S., Xu, Y., Yu, H., Wang, M., Wang, H., & Li, X. (2020). Introducing Seven Transition Metal Ions into Terpyridine-Based Supramolecules: Self-Assembly and Dynamic Ligand Exchange Study. Journal of the American Chemical Society, 142(4), 1811~1821. https://doi.org/10.1021/jacs.9b09497
García, M. D., Alvariño, C., López-Vidal, E. M., Rama, T., Peinador, C., & Quintela, J. M. (2014). Complexation of aromatic compounds with self-assembled PdII and PtII metallacycles. Inorganica Chimica Acta, 417, 27~37. https://doi.org/10.1016/j.ica.2013.10.037
Cook, T. R., Zheng, Y.-R., & Stang, P. J. (2013). Metal–Organic Frameworks and Self-Assembled Supramolecular Coordination Complexes: Comparing and Contrasting the Design, Synthesis, and Functionality of Metal–Organic Materials. Chemical Reviews, 113(1), 734~777. https://doi.org/10.1021/cr3002824
Hassanian-Moghaddam, D., Aboudzadeh, M. A., & Ahmadi, M. (2025). Strategies for designing luminescent Metallo-supramolecular polymer networks. Coordination Chemistry Reviews, 540, 216796. https://doi.org/10.1016/j.ccr.2025.216796
Sepehrpour, H., Fu, W., Sun, Y., & Stang, P. J. (2019). Biomedically Relevant Self-Assembled Metallacycles and Metallacages. Journal of the American Chemical Society, 141(36), 14005~14020. https://doi.org/10.1021/jacs.9b06222
Saha, M. L., Yan, X., & Stang, P. J. (2016). Photophysical Properties of Organoplatinum(II) Compounds and Derived Self-Assembled Metallacycles and Metallacages: Fluorescence and its Applications. Accounts of Chemical Research, 49(11), 2527~2539. https://doi.org/10.1021/acs.accounts.6b00416
Guchhait, C., Suriyaa, V., Sahu, N., Sarkar, S. D., & Adhikari, B. (2023). Ferrocene: An exotic building block for supramolecular assemblies. Chemical Communications, 59(98), 14482~14496. https://doi.org/10.1039/D3CC03659F
Gurjar, O. P., Saini, P., Kumari, S., Atal, K., Phageria, U., & Bugalia, S. (2024). A review on recent advances of iron-based macrocyclic complexes as prominent candidate for several potential applications. Journal of the Iranian Chemical Society, 21(2), 305~326. https://doi.org/10.1007/s13738-023-02934-3
Li, Y.-L., Li, A.-J., Huang, S.-L., Vittal, J. J., & Yang, G.-Y. (2023). Polypyridyl Ru( ii ) or cyclometalated Ir( iii ) functionalized architectures for photocatalysis. Chemical Society Reviews, 52(14), 4725~4754. https://doi.org/10.1039/D3CS00053B
Kurpik, G., Wachowicz, W., Walczak, A., Harrowfield, J., & Stefankiewicz, A. R. (2025). Pyridyl-β-diketonates: Versatile ligands for generation of functional nanostructures. Coordination Chemistry Reviews, 539, 216762. https://doi.org/10.1016/j.ccr.2025.216762
Sun, Y., Chen, C., & Stang, P. J. (2019). Soft Materials with Diverse Suprastructures via the Self-Assembly of Metal–Organic Complexes. Accounts of Chemical Research, 52(3), 802~817. https://doi.org/10.1021/acs.accounts.8b00663
Ghosh, K., Hu, J., White, H. S., & Stang, P. J. (2009). Construction of Multifunctional Cuboctahedra via Coordination-Driven Self-Assembly. Journal of the American Chemical Society, 131(19), 6695~6697. https://doi.org/10.1021/ja902045q
Lee, J., Ghosh, K., & Stang, P. J. (2009). Stoichiometric Control of Multiple Different Tectons in Coordination-Driven Self-Assembly: Preparation of Fused Metallacyclic Polygons. Journal of the American Chemical Society, 131(34), 12028~12029. https://doi.org/10.1021/ja903330j
Tian, Y., Yan, X., Saha, M. L., Niu, Z., & Stang, P. J. (2016). Hierarchical Self-Assembly of Responsive Organoplatinum(II) Metallacycle–TMV Complexes with Turn-On Fluorescence. Journal of the American Chemical Society, 138(37), 12033~12036. https://doi.org/10.1021/jacs.6b07402
Zhou, Z., Chen, D.-G., Saha, M. L., Wang, H., Li, X., Chou, P.-T., & Stang, P. J. (2019). Designed Conformation and Fluorescence Properties of Self-Assembled Phenazine-Cored Platinum(II) Metallacycles. Journal of the American Chemical Society, 141(13), 5535~5543. https://doi.org/10.1021/jacs.9b01368
Chen, W., Chen, Z., Chi, Y., & Tian, W. (2023). Double Cation−π Directed Two-Dimensional Metallacycle-Based Hierarchical Self-Assemblies for Dual-Mode Catalysis. Journal of the American Chemical Society, 145(36), 19746~19758. https://doi.org/10.1021/jacs.3c05143
Chen, W., Li, X., Liu, C., He, J., Qi, M., Sun, Y., Shi, B., Sepehrpour, H., Li, H., Tian, W., & Stang, P. J. (2020). β-Cyclodextrin modified Pt(II) metallacycle-based supramolecular hyperbranched polymer assemblies for DOX delivery to liver cancer cells. Proceedings of the National Academy of Sciences, 117(49), 30942~30948. https://doi.org/10.1073/pnas.2007798117
Shi, B., Zhou, Z., Vanderlinden, R. T., Tang, J.-H., Yu, G., Acharyya, K., Sepehrpour, H., & Stang, P. J. (2019). Spontaneous Supramolecular Polymerization Driven by Discrete Platinum Metallacycle-Based Host–Guest Complexation. Journal of the American Chemical Society, 141(30), 11837~11841. https://doi.org/10.1021/jacs.9b06181
Poole Iii, D. A., Bobylev, E. O., Mathew, S., & Reek, J. N. H. (2022). Entropy directs the self-assembly of supramolecular palladium coordination macrocycles and cages. Chemical Science, 13(34), 10141~10148. https://doi.org/10.1039/D2SC03154J
Kennedy, A. R., Klett, J., McGrath, G., Mulvey, R. E., Robertson, G. M., Robertson, S. D., & O’Hara, C. T. (2014). Synthesis of an alkylmagnesium amide and interception of a ring-opened isomer of the important utility amide 2,2,6,6-tetramethylpiperidide (TMP). Inorganica Chimica Acta, 411, 1~4. https://doi.org/10.1016/j.ica.2013.11.015
Buchanan, J. S., Pollard, B. L., Shen, P., Preston, D., & Connal, L. A. (2025). Selective Sequestration of Palladium(II) Cations Using a Supramolecular Polymer Approach. Chemistry – A European Journal, 31(31), e202500392. https://doi.org/10.1002/chem.202500392
Xiao, X.-Q., Jia, A.-Q., Lin, Y.-J., & Jin, G.-X. (2010). Self-Assembly of Palladium-Based Macrocycles with N-Heterocyclic Carbene as the “Corner” Ligand. Organometallics, 29(21), 4842~4848. https://doi.org/10.1021/om100040g
Bera, S., Dutta, A., & Dastidar, P. (2024). Developing Supramolecular Metallogel Derived from Pd2 L4 Cage Molecule for Delivering an Anti‐Cancer Drug to Melanoma Cell B16−F10. Chemistry – An Asian Journal, 19(17), e202400419. https://doi.org/10.1002/asia.202400419
Duan, Y.-M., Wang, K.-P., Zhang, Q., Chen, S., & Hu, Z.-Q. (2022). Artificial light-harvesting systems based on self-assembled fluorescent palladium(II)-metallacycle in aqueous solution. Dyes and Pigments, 207, 110749. https://doi.org/10.1016/j.dyepig.2022.110749
Peinador, C., Pía, E., Blanco, V., García, M. D., & Quintela, J. M. (2010). Complexation of Pyrene in Aqueous Solution with a Self-Assembled Palladium Metallocycle. Organic Letters, 12(7), 1380~1383. https://doi.org/10.1021/ol1004577
Wang, L., Zhang, Z., Jiang, X., Irvin, J. A., Liu, C., Wang, M., & Li, X. (2018). Self-Assembly of Tetrameric and Hexameric Terpyridine-Based Macrocycles Using Cd(II), Zn(II), and Fe(II). Inorganic Chemistry, 57(7), 3548~3558. https://doi.org/10.1021/acs.inorgchem.7b02361
Constable, E. C., Housecroft, C. E., & Smith, C. B. (2003). Self-assembly of two discrete polynuclear iron(II) metallomacrocycles from a ligand containing two 2,2′:6′,2″-terpyridine binding domains. Inorganic Chemistry Communications, 6(8), 1011~1013. https://doi.org/10.1016/S1387-7003(03)00168-0
Rajadurai, C., Fuhr, O., Kruk, R., Ghafari, M., Hahn, H., & Ruben, M. (2007). Above room temperature spin transition in a metallo-supramolecular coordination oligomer/polymer. Chemical Communications, (25), 2636. https://doi.org/10.1039/b702468a
Newkome, G. R., Cho, T. J., Moorefield, C. N., Cush, R., Russo, P. S., Godínez, L. A., Saunders, M. J., & Mohapatra, P. (2002). Hexagonal Terpyridine–Ruthenium and –Iron Macrocyclic Complexes by Stepwise and Self-Assembly Procedures. Chemistry - A European Journal, 8(13), 2946. https://doi.org/10.1002/1521-3765(20020703)8:13%253C2946::AID-CHEM2946%253E3.0.CO;2-M
Wang, J., Li, X., Lu, X., Chan, Y., Moorefield, C. N., Wesdemiotis, C., & Newkome, G. R. (2011). Dendron‐Functionalized Bis(terpyridine)–Iron(II) or –Cadmium(II) Metallomacrocycles: Synthesis, Traveling‐Wave Ion‐Mobility Mass Spectrometry, and Photophysical Properties. Chemistry – A European Journal, 17(17), 4830~4838. https://doi.org/10.1002/chem.201003681
Reger, D. L., Watson, R. P., Gardinier, J. R., Smith, M. D., & Pellechia, P. J. (2006). Metallacycles of Iron, Zinc, and Cadmium Assembled by Polytopic Bis(pyrazolyl)methane Ligands and Fluoride Abstraction from BF4-. Inorganic Chemistry, 45(25), 10088~10097. https://doi.org/10.1021/ic0613154
Chakrabarty, R., & Stang, P. J. (2012). Post-assembly Functionalization of Organoplatinum(II) Metallacycles via Copper-free Click Chemistry. Journal of the American Chemical Society, 134(36), 14738~14741. https://doi.org/10.1021/ja3070073
Mebi, C. A., & Gerasimchuk, N. N. (2020). Macrocyclic tetranuclear double-butterfly Fe/S carbonyl clusters as [FeFe]-hydrogenase models. Supramolecular Chemistry, 32(11), 557~568. https://doi.org/10.1080/10610278.2020.1837828
Newkome, G. R., Cho, T. J., Moorefield, C. N., Mohapatra, P. P., & Godínez, L. A. (2004). Towards Ordered Architectures: Self‐Assembly and Stepwise Procedures to the Hexameric Metallomacrocycles [Arylbis(terpyridinyl)6 FeII 6− n ‐RuIIn ] ( n =0,2,3,5). Chemistry – A European Journal, 10(6), 1493~1500. https://doi.org/10.1002/chem.200305267
Rota Martir, D., & Zysman-Colman, E. (2018). Supramolecular iridium(III) assemblies. Coordination Chemistry Reviews, 364, 86~117. https://doi.org/10.1016/j.ccr.2018.03.016
Zhang, Q., Chen, Y., & Liu, C. (2025). Living supramolecular polymerization of Ir(III) complexes. Molecular Chemistry & Engineering, 1(1), 100008. https://doi.org/10.1016/j.mochem.2025.100008
Li, X., Chan, Y.-T., Casiano-Maldonado, M., Yu, J., Carri, G. A., Newkome, G. R., & Wesdemiotis, C. (2011). Separation and Characterization of Metallosupramolecular Libraries by Ion Mobility Mass Spectrometry. Analytical Chemistry, 83(17), 6667~6674. https://doi.org/10.1021/ac201161u
Hwang, S.-H., Moorefield, C. N., Wang, P., Kim, J.-Y., Lee, S.-W., & Newkome, G. R. (2007). Synthesis and photophysical properties for fluorescent hexameric metallomacrocycles: Zinc(II)-mediated self-assembly of bis(terpyridine) ligands. Inorganica Chimica Acta, 360(5), 1780~1784. https://doi.org/10.1016/j.ica.2006.09.012
Li, H., Yao, Z.-J., Liu, D., & Jin, G.-X. (2015). Multi-component coordination-driven self-assembly toward heterometallic macrocycles and cages. Coordination Chemistry Reviews, 293~294, 139~157. https://doi.org/10.1016/j.ccr.2014.08.014
Pal, P., Datta, A., Jana, R., Datta, A., & Malik, S. (2023). Solid-state emissive Zn2+ directed metallo-supramolecular polymers of bis-terpyridine appended aryl substituted buta-1,3-diene derivatives: Synthesis, photo-physical and electrochemical properties. European Polymer Journal, 194, 112115. https://doi.org/10.1016/j.eurpolymj.2023.112115
Bera, M. K., Sarmah, S., Santra, D. C., & Higuchi, M. (2024). Heterometallic supramolecular polymers: From synthesis to properties and applications. Coordination Chemistry Reviews, 501, 215573. https://doi.org/10.1016/j.ccr.2023.215573
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Copyright (c) 2026 Zihao Du, Shengqiang Li, Tianyi Wang, Ruihua Mu, Jin Liu, Zhenhao Wang, Weitao Yuan, Yang Dong, Wenzhuo Chen

This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.
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Accepted: 2026-08-04
Published: 2026-09-03







