功能超分子配合物化学与材料中Salamo/Salen类体系的构筑与性能研究进展
Progress in the Construction and Properties of Salamo/Salen-Based Systems in Functional Supramolecular Coordination Chemistry and Materials
摘要: Salamo/Salen类配体因具有可设计的多齿配位空腔、较好的结构可调性以及优异的光学响应性能，已成为功能超分子配合物化学与材料研究中的重要构筑单元。相较于传统salen体系，Salamo/half-salamo/bis(Salamo)及其杂化衍生物通过引入氧肟键显著提升了配体稳定性，并进一步拓展了不对称配体、柔性链桥和多腔体结构的构筑空间。近年来，相关研究已从单纯的配位结构报道发展到多核与异核组装、超分子弱相互作用调控、荧光/比色识别、理论计算辅助解析及环境与生物应用等多个层面。本文结合已提供文献，对Salamo/Salen类体系的结构演化、同核和异核多核配合物的构筑规律、阴离子/溶剂/辅助配体的结构导向作用、荧光识别与多通道响应机制、DFT/TD-DFT与Hirshfeld表面分析在机理研究中的作用以及试纸、水样、植物和斑马鱼等实际应用进行了系统综述。总体来看，该类体系在结构可设计性、功能集成性和应用可拓展性方面显示出明显优势，但在普适构效关系建立、纯水体系稳定性、生物相容性和器件化等方面仍存在进一步提升空间。本文最后对该领域未来向多功能集成、原位可视化检测、智能响应材料和更高层级超分子体系发展的趋势进行了展望。
Abstract: Salamo/Salen-type ligands, with their designable multidentate coordination cavities, excellent structural tunability, and superior optical response properties, have emerged as crucial building blocks in the chemistry and materials research of functional supramolecular complexes. Compared to traditional salen systems, Salamo/half-salamo/bis(Salamo) and their hybrid derivatives significantly enhance the stability of the ligands by introducing hydroxamate bonds, further expanding the construction space for asymmetric ligands, flexible chain bridges, and multi-cavity structures. In recent years, related research has evolved from the mere reporting of coordination structures to multiple levels, including polynuclear and heteronuclear assembly, regulation of supramolecular weak interactions, fluorescence/colorimetric recognition, theoretical calculation-assisted analysis, as well as environmental and biological applications. Based on the published literatures, this paper systematically reviews the structural evolution of Salamo/Salen-based systems, the construction rules of homonuclear and heteronuclear polynuclear complexes, the structure-directing effects of anions/solvents/auxiliary ligands, the mechanisms of fluorescence recognition and multi-channel response, the roles of DFT/TD-DFT and Hirshfeld surface analysis in mechanistic studies, as well as their practical applications in test papers, water samples, plants, and zebrafish. Overall, these systems exhibit obvious advantages in structural designability, functional integration, and application expandability. However, there remains room for further improvement in the establishment of universal structure-activity relationships, the stability in pure water systems, biocompatibility, and device fabrication. Finally, the paper prospects the future development trends of this field towards multi-functional integration, in-situ visualization detection, intelligent responsive materials, and higher-level supramolecular systems.
文章引用：蔡张, 杨晓雯, 李小刚. 功能超分子配合物化学与材料中Salamo/Salen类体系的构筑与性能研究进展[J]. 物理化学进展, 2026, 15(3): 279-288. https://doi.org/10.12677/japc.2026.153027

参考文献

[1] Akine, S., Taniguchi, T., Dong, W., Masubuchi, S. and Nabeshima, T. (2005) Oxime-Based Salen-Type Tetradentate Ligands with High Stability against Imine Metathesis Reaction. The Journal of Organic Chemistry, 70, 1704-1711.
https://doi.org/10.1021/jo048030y
[2] Dong, W.K., Zhang, J.Q. and Du, M.X. (2022) A Highly Selective and Sensitive Salamo-Salen-Salamo Hybrid Fluorometic Chemosensor for Identification of Zn2+ and the Continuous Recognition of Phosphate Anions. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 278, Article ID: 121340.
https://doi.org/10.1016/j.saa.2022.121340
[3] Li, R.Y., Gao, S.X., Liu, C., Dong, W. and Ding, Y. (2022) Dual-Channel More Flexible Salamo-Like Chemosensor for Fluorogenic Sensing of Copper Ion in Semi-Aqueous Medium. Journal of Applied Spectroscopy, 89, 177-185.
https://doi.org/10.1007/s10812-022-01341-5
[4] Feng, L.C., Zhang, J., Dou, L. and Dong, W. (2023) Synthesis, Structure, Theoretical Studies, and Fluorescence Properties of Two Multinuclear Cu(II) Bis(salamo)-Like Complexes. Journal of Coordination Chemistry, 76, 648-666.
https://doi.org/10.1080/00958972.2023.2210740
[5] Liu, G.H., Li, M., Li, L., Bian, R. and Dong, W. (2022) Sequential Multiple-Target Chemosensor: Co2+, Cu2+, PPi, and HS− Discrimination by a Bis(half-salamo)-Type Probe. Phosphorus, Sulfur, and Silicon and the Related Elements, 197, 124-132.
https://doi.org/10.1080/10426507.2021.2012674
[6] Yue, Y.N., La, Y.T., Han, X.J. and Dong, W. (2022) Coordination-Driven Self-Assemblies of Two Hetero‐Trinuclear [Cu(II)2Ln(III)] (Ln = La and Ce) Complexes with a Flexible Bis(salamo)‐Type Ligand. Journal of Coordination Chemistry, 75, 413-430.
https://doi.org/10.1080/00958972.2022.2050713
[7] Zhang, T., Li, P., Li, L. and Dong, W. (2022) An Investigation into Luminescent Phenoxo-Bridged Heterobimetallic Copper(II)-Calcium(II)/Strontium(II)-Based Bis(salamo)-Like Complexes. Transition Metal Chemistry, 47, 53-65.
https://doi.org/10.1007/s11243-021-00489-x
[8] Yue, Y.N., Zhang, T., La, Y.T. and Dong, W. (2022) An Exploration of Structurally Characterized Hetero-Trinuclear [Cu(II)2Ca(II)] Flexible-Bis(salamo)-Type Complex. Journal of Structural Chemistry, 63, 854-867.
https://doi.org/10.1134/s0022476622060026
[9] Yue, Y.N., La, Y.T., Zhang, J. and Dong, W. (2022) Synthesis, Crystal Structure, Fluorescence Properties and Theoretical Calculations of Heterobimetallic 3d-4f Complex with a Flexible Bis(salamo)‐Type Ligand. Journal of Molecular Structure, 1264, Article ID: 133272.
https://doi.org/10.1016/j.molstruc.2022.133272
[10] Zhang, T., Li, W., Li, X., Peng, Y. and Dong, W. (2022) Unusual Fluorescence Behavior of First 3d-3d’ Heterobimetallic [Cu(II)2Mn(II)] Complex Bearing a Bis(salamo)-Based Ligand. Journal of Molecular Structure, 1260, Article ID: 132854.
https://doi.org/10.1016/j.molstruc.2022.132854
[11] Feng, S.S., Li, L.L., Li, P. and Dong, W. (2022) Construction of Novel Hexanuclear Co(II) and Dinuclear Ni(II) Bis(salamo)‐Type Complexes. Applied Organometallic Chemistry, 36, e6501.
https://doi.org/10.1002/aoc.6501
[12] Li, R., Dou, L., Tong, L. and Dong, W. (2022) Exploring Two Helical Centrosymmetric Homotetranuclear Cu(II) Bis(salamo)‐Based Complexes. Applied Organometallic Chemistry, 36, e6671.
https://doi.org/10.1002/aoc.6671
[13] Deng, Y.H., Yan, Y.J., Zhang, J., Na, L., Zhang, Y. and Dong, W. (2022) Exploitation of a Half-Conjugate Polydentate Salamo-Salen Hybrid Ligand and Its Two Phenoxide-Bridged Heterohexanuclear 3d-s Double-Helical Cluster Complexes. Inorganic Chemistry, 61, 1018-1030.
https://doi.org/10.1021/acs.inorgchem.1c03066
[14] Li, L.L., Feng, S.S., Zhang, T., Wang, L. and Dong, W. (2022) Counteranion-Solvent-Dependent Construction of Two Octahedral Homopolynuclear Ni(II) Complexes with a Symmetrical Multi-Halogen-Substituted Bis(salamo)-Based Ligand. Inorganica Chimica Acta, 534, Article ID: 120815.
https://doi.org/10.1016/j.ica.2022.120815
[15] Li, M., Li, L.L., Li, P. and Dong, W. (2022) Supramolecular Assemblies in an Unprecedented Asymmetric Salamo-Based Dinuclear Nickel(II) Complex Bearing Two Different Coordination Modes. Journal of Structural Chemistry, 63, 280-292.
https://doi.org/10.1134/s0022476622020093
[16] Li, S.Z., Wei, Y.X., Huang, Y. and Dong, W. (2022) Counteranion-Driven Self-Assembly of Di-and Tetra-Nuclear Zn(II) Single‐Armed Salamo‐Type Complexes. Journal of Molecular Structure, 1265, Article ID: 133473.
https://doi.org/10.1016/j.molstruc.2022.133473
[17] Li, M., Li, S., Huang, Y. and Dong, W. (2022) A Dual-Channel Chemosensor Based on 2-Hydroxy-5-methyl-1,3-benzenedialdehyde for Fluorescence Detection and Colorimetric Recognition of Glutamic Acid. Journal of Photochemistry and Photobiology A: Chemistry, 431, Article ID: 114053.
https://doi.org/10.1016/j.jphotochem.2022.114053
[18] Na, L., Dou, L., Yan, Y., Li, R. and Dong, W. (2022) A New Reversible Aldehyde-Appended Salamo-Like Fluorogenic Probe for Cascade Sensing of Ni2+ and HPO2− 4 Ions in Aqueous Medium. Journal of Photochemistry and Photobiology A: Chemistry, 432, Article ID: 114061.
https://doi.org/10.1016/j.jphotochem.2022.114061
[19] Man, L.L., Dou, L., Li, W., La, Y. and Dong, W. (2022) A Dual-Signal Half-Salamo-Based Sensing Platform for Simultaneous Colorimetric and Fluoremetric Detection of Fe3+ and Reversible Recognition of OH− Ions. Journal of Photochemistry and Photobiology A: Chemistry, 431, Article ID: 114068.
https://doi.org/10.1016/j.jphotochem.2022.114068
[20] Huang, Y., Li, X., Li, W. and Dong, W. (2023) Experimental and Theoretical Investigation of a New Non-Symmetric Salamo-Like Ligand and Its Tri-Nuclear Zn(II) and Ni(II) Complexes. Inorganica Chimica Acta, 546, Article ID: 121303.
https://doi.org/10.1016/j.ica.2022.121303
[21] Hu, Z.F., Chai, Z.L., Zhou, Q., Feng, L., Dong, W. and Ding, Y. (2023) The First Salamo-Type Mixed-Ligand Cu(II) Coordination Polymer: Synthesis, Crystal Structure and Theoretical Studies. Journal of Molecular Structure, 1287, Article ID: 135709.
https://doi.org/10.1016/j.molstruc.2023.135709
[22] Wei, Y.X., Zheng, Y.R., Niu, H.Y., et al. (2023) Synthesis, Structure, Properties and Theoretical Studies of Novel Tetranuclear Nickel(II) Bis(salamo)-Like Complex. Journal of Molecular Structure, 1288, Article ID: 135812.
https://doi.org/10.1016/j.molstruc.2023.135812
[23] Zhang, Y., Tong, L., Li, X., Dou, L., Cheng, H., Dong, W., et al. (2023) A Novel Structurally Characterized 4,4’-Bipyridine-Salamo-Like Nickel(II) Coordination Polymer Fluorescence Probe for Selective Sensing of Cr2O2− 7 and 4-Nitrophenol. Journal of Molecular Structure, 1289, Article ID: 135868.
https://doi.org/10.1016/j.molstruc.2023.135868
[24] Guo, W., Ji, T., Ma, Y., Song, H., Liu, J. and Dong, W. (2023) An Amino-Appended Asymmetry Salamo-Type Ratiometric Fluorescent Probe for Efficient Relay Detection of B4O2− 7/HCHO in Real Samples. Journal of Molecular Structure, 1285, Article ID: 135545.
https://doi.org/10.1016/j.molstruc.2023.135545
[25] Huang, Y., Ding, Y., Zheng, Y., Sun, Y. and Dong, W. (2023) An Asymmetric Salamo-Type Fluorescent Chemosensor for Efficient Recognition of Cu2+ and B4O2− 7 Ions. Journal of Molecular Structure, 1292, Article ID: 136132.
https://doi.org/10.1016/j.molstruc.2023.136132
[26] Guo, W.T., Ji, T.X., Ma, Y., Hu, Z., Song, H., Liu, J., et al. (2023) A Highly Sensitive and Selective “On-Off-On” Salamo-Like Fluorescent Sensor for Relay Recognition of ClO− and SCN−. Journal of Molecular Structure, 1292, Article ID: 136164.
https://doi.org/10.1016/j.molstruc.2023.136164
[27] Zhao, L., Niu, H., Zheng, Y., Wei, Y., Zhang, J., Dong, W., et al. (2023) Unusual Bi-and Tetra-Nuclear Cobalt(II) Bis(salamo)-Based Complex: Preparation, Crystal Structure and Theoretical Calculations and Fluorescence Properties. Journal of Molecular Structure, 1293, Article ID: 136237.
https://doi.org/10.1016/j.molstruc.2023.136237
[28] Tong, L., Man, L., Li, X. and Dong, W. (2023) Two Novel Quinoline-Decorated Half-Salamo-Type Co(II) Complexes: Synthesis, Crystal Structure, Hirshfeld Surface Analysis, DFT Calculation and Fluorescence Properties. Journal of Molecular Structure, 1294, Article ID: 136372.
https://doi.org/10.1016/j.molstruc.2023.136372
[29] La, Y.T., Du, M.X., Gan, L.L., Zhang, Y., Sun, Y. and Dong, W. (2024) Spectroscopic and Theoretical Studies on a Novel Bis(salamo)-Like Probe for Highly Effective Fluorimetric-Colorimetric Identification of Fe3+ and Cu2+ in Aquo-Organic Medium. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 305, Article ID: 123481.
https://doi.org/10.1016/j.saa.2023.123481
[30] Peng, Y.D., Ding, Y.F., Zheng, Y.R., Chai, Z., Wei, Y., Wang, L., et al. (2023) Spectroscopic and Theoretical Studies on a Rare and Rigid Bis(salamo)-Like Fluorescent Probe for the Sequential Recognition of Cu2+ and HSO− 4 Ions. Inorganic Chemistry Communications, 158, Article ID: 111598.
https://doi.org/10.1016/j.inoche.2023.111598
[31] Hu, Z.F., Chai, Z.L., Zheng, Y.R., Ding, Y., Dong, W. and Ding, Y. (2023) A Unique AIE Multi-Responsive Half-Salamo-Like Fluorescence Sensor for Temperature, pH and Cu2+/S− 2 Ions in Aqueous Media. Microchemical Journal, 190, Article ID: 108736.
https://doi.org/10.1016/j.microc.2023.108736
[32] Na, L., Feng, L.C., Feng, S. and Dong, W. (2022) A Novel Fluorometric and Colorimetric Dual-Channel Single-Armed Salamo-Like Chemosensor for the Fast, Reversible and Simultaneous Detection of Fe3+ and Cu2+ Ions. Inorganica Chimica Acta, 537, Article ID: 120932.
https://doi.org/10.1016/j.ica.2022.120932
[33] Zhang, Y., Li, W., Ma, C. and Dong, W. (2023) A Pyridine-Appended Half-Salamo-Based Fluorescent Chemosensor for Efficiently and Selectively Sensing Cu2+ Ions. Inorganica Chimica Acta, 556, Article ID: 121651.
https://doi.org/10.1016/j.ica.2023.121651
[34] Zhang, Y., Li, S.Z., Yan, Y.B., Dou, L. and Dong, W. (2023) Structurally Novel Bi-Nuclear Cobalt(III) Complex Self-Assembled by a Single-Armed Salamo-Like Ligand. Chemical Papers, 77, 6255-6266.
https://doi.org/10.1007/s11696-023-02935-9
[35] Zhang, T., Yue, Y.N., Li, W.D. and Dong, W. (2023) Newly Designed Heterotrinuclear [Zn(II)2Ln(III)] Complexes Constructed from a Flexible C-Shaped Bis(salamo)-Based Ligand. Russian Journal of General Chemistry, 93, 962-971.
https://doi.org/10.1134/s1070363223040254
[36] Li, P., Li, S., Dou, L. and Dong, W. (2023) Synthesis and Crystal Structure of Zero-Dimensional Trinuclear Ni(II) Salamo-Type Complex Involving a Variety of Interactions. Russian Journal of General Chemistry, 93, 972-980.
https://doi.org/10.1134/s1070363223040266
[37] Li, L., Ma, C.Y., Hu, Z.F., et al. (2023) Synthesis, Crystal Structure, Fluorescence Property, and Theoretical Investigation of Counteranion-Introduced Ni(II) Complex with Pyridine-Appended Half-Salamo-Like Ligand. Russian Journal of Inorganic Chemistry, 68, 1293-1302.
https://doi.org/10.1134/s0036023623601198
[38] Zhang, Y., Feng, L.C., Li, X.X. and Dong, W. (2023) Synthesis, Crystal Structure, and Theoretical Calculations of a Μ-Dichloro-Bridged Tetranuclear Cu(II) Bis(salamo)-Type Complex. Russian Journal of General Chemistry, 93, 1486-1497.
https://doi.org/10.1134/s107036322306021x
[39] Li, S., Dou, L., Huang, Y., Li, P. and Dong, W. (2022) Multinuclear Co(II) and Zn(II) Salamo-Based Complexes with Unique Τ5 Parameters: Structure Characterizations, Hirshfeld Surfaces and Fluorescence Properties. Polyhedron, 212, Article ID: 115615.
https://doi.org/10.1016/j.poly.2021.115615
[40] Man, L.L., Ding, Y.F., Li, X., Tong, L. and Dong, W. (2023) Exploring the Structural Diversities of Three Co(II) Complexes Constructed from a New Quinoline-Containing N3O-Cavity Half-Salamo Type Ligand and Various Counteranions. Polyhedron, 245, Article ID: 116654.
https://doi.org/10.1016/j.poly.2023.116654
[41] Li, X.X., Du, M.X., Ma, C.Y., Dong, W. and Ding, Y. (2024) A More Flexible Long-Chain Bis(salamo)-Like Fluorescent Probe Based on FRET and ICT Effects for the Identification of Aluminum Ion in the Environment and Plants. Journal of Molecular Structure, 1295, Article ID: 136792.
https://doi.org/10.1016/j.molstruc.2023.136792
[42] Li, X.X., Ma, C.Y., Du, M.X., Dong, W. and Ding, Y. (2024) A Rare Salamo-Salophen Type “On-Off-On” Fluorescent Probe for Relay Recognition of Hg2+ and Phosphate Ions and Its Applications. Journal of Molecular Structure, 1299, Article ID: 137188.
https://doi.org/10.1016/j.molstruc.2023.137188
[43] La, Y.T., Yan, Y.J., Li, X., Zhang, Y., Sun, Y. and Dong, W. (2024) A Novel Salamo-Salen-Salamo Hybrid Mg(II) Complex Fluorescent Chemosensor for Highly Effective Monitoring H2PO− 4 in Zebrafish and Plants. Journal of Molecular Structure, 1295, Article ID: 136641.
https://doi.org/10.1016/j.molstruc.2023.136641
[44] Man, L., Wang, G., Wei, X., Xu, C., Tong, L., Zhang, Y., et al. (2024) Spectroscopic Properties of a Fluorescent Pyrene-Quinoline-Based Bisoxime-Type Sensor and Its Application to the Detection of Cu2+ Ion in Real Water Samples. Journal of Molecular Structure, 1309, Article ID: 138131.
https://doi.org/10.1016/j.molstruc.2024.138131
[45] Zhang, Y., Su, Y., Cai, Z., Tong, L. and Dong, W. (2024) Structural, Fluorescent and Theoretical Studies of a More Flexible Salamo-Type Ligand and Its Uncommon Tetranuclear Chloride-Bridged Nickel(II) Complex. Journal of Molecular Structure, 1309, Article ID: 138164.
https://doi.org/10.1016/j.molstruc.2024.138164
[46] Zhang, J.Q., Yao, G.X., La, Y.T. and Dong, W. (2022) A Highly Selective Bis(salamo)-Based Fluorescent Sensor for Two-Pronged Recognitions to Cu2+ and Arg. Inorganica Chimica Acta, 533, Article ID: 120775.
https://doi.org/10.1016/j.ica.2021.120775
[47] Feng, S.S., Wei, Y.X., Li, M. and Dong, W. (2022) A Highly Selective Naphthalene-Fluorophore Salamo-Based Chemosensor for Sequential Identification of Cu2+ and S− 2 Ions in Water Applications. Journal of Molecular Structure, 1261, Article ID: 132923.
https://doi.org/10.1016/j.molstruc.2022.132923
[48] Ding, Y.F., La, Y.T., Li, W.D., et al. (2021) Experimental and Theoretical Studies of Two New Trinuclear Ni(II) Asymmetric Salamo-Based Complexes. Russian Journal of General Chemistry, 91, S89-S97.
https://doi.org/10.1134/s1070363222020220
[49] Li, M., Feng, L.C., Feng, S.S. and Dong, W. (2022) A Nonsymmetric Salamo-Based Turn-Off Fluorescent Probe for the Detection of Cu2+ and Its Structurally Rare Dinuclear Cu(II) Complex. Journal of Molecular Structure, 1261, Article ID: 132926.
https://doi.org/10.1016/j.molstruc.2022.132926
[50] Wang, S., Liao, Y.H., Feng, H.J., Wu, L. and He, W. (2024) The Studies on a Fluorescent Probe of Schiff Base Modified by 1,2,3-Triazole to Detecting Al3+ and Living Cell Imaging. Journal of Molecular Structure, 1296, Article ID: 136730.
https://doi.org/10.1016/j.molstruc.2023.136730