Auxiliary Ligand Effects on Metal Coordination Polymer Properties
Main Article Content
Abstract
Coordination polymers have emerged as versatile materials with tunable structural and functional properties that can be systematically modified through rational design strategies. The incorporation of auxiliary ligands alongside primary bridging ligands represents a powerful synthetic approach for controlling the dimensionality, topology, and physicochemical characteristics of these materials. This review examines how auxiliary ligands influence the structural assembly and functional properties of metal coordination polymers, with particular emphasis on multicarboxylate-based systems. The discussion encompasses synthetic methodologies, structural diversity, and property modulation including magnetic behavior, luminescence, catalytic activity, and biological applications. Through analysis of recent developments in mixed-ligand coordination polymer design, this work demonstrates how secondary ligands containing nitrogen-donor atoms, particularly imidazole derivatives, can direct framework formation and enhance material performance. The interplay between metal centers, primary carboxylate ligands, and auxiliary nitrogen-containing ligands creates opportunities for developing coordination polymers with predetermined structures and optimized properties for applications in energy storage, catalysis, sensing, and biomedicine.
Article Details
Section
How to Cite
References
1. G. Xie, W. Guo, Z. Fang, Z. Duan, X. Lang, and D. Liu et al., “Dual‐metal sites drive tandem electrocatalytic CO2 to C2+ products,” Angewandte Chemie, vol. 136, no. 47, p. e202412568, 2024, doi: 10.1002/ange.202412568.
2. I. Dragutan, F. Ding, Y. Sun, and V. Dragutan, “Recent Developments in Multifunctional Coordination Polymers,” Crystals, vol. 14, no. 4, p. 301, 2024, doi: 10.3390/cryst14040301.
3. J.-Q. Liu, Z.-D. Luo, Y. Pan, A. Kumar Singh, M. Trivedi, and A. Kumar, “Recent developments in luminescent coordination polymers: Designing strategies, sensing application and theoretical evidences,” Coordination Chemistry Reviews, vol. 406, p. 213145, 2020, doi: 10.1016/j.ccr.2019.213145.
4. M. Du, C.-P. Li, C.-S. Liu, and S.-M. Fang, “Design and construction of coordination polymers with mixed-ligand synthetic strategy,” Coordination Chemistry Reviews, vol. 257, no. 7–8, pp. 1282–1305, 2013, doi: 10.1016/j.ccr.2012.10.002.
5. T. K. Ghosh and G. R. Rao, “Design and synthesis of mixed-ligand architectured Zn-based coordination polymers for energy storage,” Dalton Transactions, vol. 52, no. 18, pp. 5943–5955, 2023, doi: 10.1039/d3dt00518f.
6. F. Ding, C. Ma, W.-L. Duan, and J. Luan, “Second auxiliary ligand induced two coppor-based coordination polymers and urease inhibition activity,” Journal of Solid State Chemistry, vol. 331, p. 124537, 2024, doi: 10.1016/j.jssc.2023.124537.
7. L. Cui, G.-P. Yang, W.-P. Wu, H.-H. Miao, Q.-Z. Shi, and Y.-Y. Wang, “Solvents and auxiliary ligands co-regulate three antiferromagnetic Co(ii) MOFs based on a semi-rigid carboxylate ligand,” Dalton Transactions, vol. 43, no. 15, pp. 5823–5830, 2014, doi: 10.1039/c3dt53342e.
8. S. Zang, Y. Su, J. Lin, Y. Li, S. Gao, and Q. Meng, “Four coordination polymers constructed from a multicarboxylate ligand and metal centers various from Ba2+, Cu2+, Zn2+ to Gd3+: Syntheses, crystal structures and properties,” Inorganica Chimica Acta, vol. 362, no. 7, pp. 2440–2446, 2009, doi: 10.1016/j.ica.2008.11.012.
9. B. Guo, L. Li, Y. Wang, Y. Zhu, and G. Li, “Construction of a series of coordination polymers from three imidazole-based multi-carboxylate ligands,” Dalton Transactions, vol. 42, no. 39, pp.14268-14280., 2013, doi: 10.1039/c3dt51486b.
10. F. Ding, N. Su, C. Ma, B. Li, W.-L. Duan, and J. Luan, “Fabrication of two novel two-dimensional copper-based coordination polymers regulated by the ‘V’-shaped second auxiliary ligands as high-efficiency urease inhibitors,” Inorganic Chemistry Communications, vol. 170, p. 113319, 2024, doi: 10.1016/j.inoche.2024.113319.
11. Y. Ma, L. Du, K. Wang, and Q. Zhao, “Synthesis, Crystal Structure, Luminescence and Magnetism of Three Novel Coordination Polymers Based on Flexible Multicarboxylate Zwitterionic Ligand,” Crystals, vol. 7, no. 1, p. 32, 2017, doi: 10.3390/cryst7010032.
12. L.-N. Zheng, L.-Y. Xu, Y.-T. Yan, T. Ding, and C.-C. Feng, “Two Cu (II) coordination polymers based on isomeric N-heterocyclic multicarboxylate ligands: Construction and magnetic properties,” Journal of Molecular Structure, vol. 1257, p. 132619, 2022, doi: 10.1016/j.molstruc.2022.132619.
13. W.-D. Li, J.-L. Li, X.-Z. Guo, Z.-Y. Zhang, and S.-S. Chen, “Metal (II) Coordination Polymers Derived from Mixed 4-Imidazole Ligands and Carboxylates: Syntheses, Topological Structures, and Properties,” Polymers, vol. 10, no. 6, p. 622, 2018, doi: 10.3390/polym10060622.
14. J. T. Lu, D. D. Meng, and Q.-G. Meng, “Assembly of Zn (II) and Cd (II) coordination polymers based on a flexible multicarboxylate ligand and nitrogen-containing auxiliary ligands through a mixed-ligand synthetic strategy: syntheses, structures and fluorescence properties,” Acta Crystallographica Section C Structural Chemistry, vol. 72, no. 2, pp. 99–104, 2016, doi: 10.1107/S2053229615023967.
15. G. Xie, Z. Zhu, D. Liu, W. Gao, Q. Gong, W. Dong, et al., “3D gas diffusion layer with dual‐metal sites for enhanced CO₂ electrolysis to C₂⁺ products,” Angewandte Chemie, vol. e202510167, 2025.