Salamo类Schiff碱过渡金属配合物的结构调控、光物理机制与功能应用综述
A Review on Structure Regulation, Photophysical Mechanisms and Functional Applications of Salamo-Related Schiff Base Transition Metal Complexes
摘要: 基于2020~2024年发表的51篇代表性文献，本文系统综述了salamo类Schiff碱过渡金属配合物在配体设计、结构调控、理论分析、光学性质与功能应用方面的研究进展。重点归纳了多腔体配体、不对称修饰、裸露甲酰基、喹啉或酰腙引入以及Salamo-Salen-Salamo杂化等设计策略，总结了溶剂、阴离子、辅助配体和原位转化对核数、构型与组装层级的调控规律，并评述了相关体系在荧光识别、聚集诱导发光、力致发光变色、光催化降解及化学动力学治疗中的应用表现。综述认为，该领域已由以新结构报道为主逐步转向结构–性质–功能协同设计，但在可预测合成、激发态机理解析和复杂环境应用等方面仍需加强。
Abstract: Based on 51 representative papers published from 2020 to 2024, this review systematically summarizes the recent progress of salamo-, half-salamo-, single-salamo-, bis(salamo)-, and Salamo-Salen-Salamo-hybrid ligand-based transition metal complexes in ligand design, structural regulation, theoretical analysis, optical properties, and functional applications. The key molecular design strategies, including multicavity construction, asymmetric modification, bare formyl-group exposure, quinoline/acylhydrazone decoration, and hybrid chain engineering, are first compared. The review then analyzes how metal-ion preferences, solvent effects, counter-anion effects, auxiliary ligands, and in situ ligand transformations jointly govern nuclearity evolution, bridging modes, supramolecular assembly, and property outputs. Particular attention is paid to the combined use of Hirshfeld surface analysis, DFT/TD-DFT, IRI, and ESP/MESP methods for revealing structure-property relationships. On this basis, the advances in fluorescence/colorimetric sensing, AIE/ESIPT behavior, luminescent mechanochromism, photocatalytic degradation, and chemodynamic therapy are critically discussed. It is concluded that this research line has evolved from structure-oriented synthesis toward mechanism-guided and application-oriented coordination design. Nevertheless, major challenges remain in predictable synthesis, excited-state mechanism elucidation, quantitative performance evaluation, and practical operation in highly aqueous or biologically relevant environments. Future progress will depend on the deep integration of multicavity hybrid-ligand design, in situ characterization, advanced computation, and scenario-oriented validation.
文章引用：蔡张, 杨晓雯, 李小刚. Salamo类Schiff碱过渡金属配合物的结构调控、光物理机制与功能应用综述[J]. 物理化学进展, 2026, 15(3): 215-226. https://doi.org/10.12677/japc.2026.153021

参考文献

[1] Chang, J., Zhang, S.Z., Wu, Y., Zhang, H.J. and Sun, Y.X. (2020) Three Supramolecular Trinuclear Nickel(II) Complexes Based on Salamo-Type Chelating Ligand: Syntheses, Crystal Structures, Solvent Effect, Hirshfeld Surface Analysis and DFT Calculation. Transition Metal Chemistry, 45, 279-293.
https://doi.org/10.1007/s11243-020-00379-8
[2] Zhang, S.Z., Guo, G., Ding, W.M., Li, J., Wu, Y., Zhang, H.J., et al. (2021) Synthesis and Spectroscopic Properties of Two Different Structural Schiff Base Zn(II) Complexes Constructed with/without Auxiliary Ligands. Journal of Molecular Structure, 1230, Article ID: 129627.
https://doi.org/10.1016/j.molstruc.2020.129627
[3] Zhang, S.Z., Chang, J., Zhang, H.J., Sun, Y.X., Wu, Y. and Wang, Y.B. (2020) Synthesis, Crystal Structure and Spectral Properties of Binuclear Ni(II) and Cubane-Like Cu4(μ3-O)4 Cored Tetranuclear Cu(II) Complexes Based on Coumarin Schiff Base. Chinese Journal of Inorganic Chemistry, 36, 503-514.
[4] Zhang, P., Xu, X., Cui, Y.F., Wei, X.H., Meng, S.J. and Sun, Y.X. (2021) A Highly Sensitive and Selective Bissalamo-Coumarin-Based Fluorescent Chemical Sensor for Cr3+/Al3+ Recognition and Continuous Recognition S2-. Journal of Photochemistry and Photobiology A: Chemistry, 408, Article ID: 113066.
https://doi.org/10.1016/j.jphotochem.2020.113066
[5] Li, S.Z., Li, W.D., Yan, Y.B., Zhang, Y. and Dong, W.K. (2022) Investigations of Stable Penta-and Hexa-Coordinate Polynuclear Zn(II) and Cd(II) Complexes Derived from a Single-Armed Salamo-Based Ligand. Journal of Coordination Chemistry, 76, 28-44.
https://doi.org/10.1080/00958972.2022.2159396
[6] Yue, Y.N., La, Y.T., Zhang, J. and Dong, W.K. (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
[7] Li, M., Li, S.Z., Huang, Y. and Dong, W.K. (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
[8] Na, L.P., Dou, L., Yan, Y.J., Li, R.Y. and Dong, W.K. (2022) A New Reversible Aldehyde-Appended Salamo-Like Fluorogenic Probe for Cascade Sensing of Ni2+ and HPO42− Ions in Aqueous Medium. Journal of Photochemistry and Photobiology A: Chemistry, 432, Article ID: 114061.
https://doi.org/10.1016/j.jphotochem.2022.114061
[9] Man, L.L., Dou, L., Li, W.D., La, Y.T. and Dong, W.K. (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
[10] Li, S.Z., Wei, Y.X., Huang, Y. and Dong, W.K. (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
[11] Han, X.J., Yan, Y.J., Dou, L., Peng, Y.D., Huang, F. and Dong, W.K. (2022) The Investigation on First Co(III) Pyridine-Including Half-Salamo-Like Complexes. Journal of Molecular Structure, 1265, Article ID: 133475.
https://doi.org/10.1016/j.molstruc.2022.133475
[12] Li, S.Z., Tong, L., Li, X. and Dong, W.K. (2022) New Insight into Two Penta-Coordinated Multinuclear Copper(II) Single-Armed Salamo-Based Complexes. Inorganica Chimica Acta, 540, Article ID: 121047.
https://doi.org/10.1016/j.ica.2022.121047
[13] Feng, L.C., Dou, L., Li, X.X. and Dong, W.K. (2022) Investigation of Two Novel di-and Tetra-Nuclear Cu(II) Bis(Salamo)-Type Complexes. Polyhedron, 224, Article ID: 116024.
https://doi.org/10.1016/j.poly.2022.116024
[14] Zhang, J., Feng, L.C., Li, S.Z. and Dong, W.K. (2022) Studies on Two Phenoxo-Bridged Homopolynuclear Cu(II) Bis(Salamo) Type Complexes Based on Theoretical Calculations and Fluorescence Properties. Polyhedron, 226, Article ID: 116113.
https://doi.org/10.1016/j.poly.2022.116113
[15] Dou, L., Tong, L., Yan, Y.B., Deng, Y.H. and Dong, W.K. (2022) Experimental and Theoretical Study of a Sandwich-Like Phenoxo-Bridged Heterobimetallic Zinc(II)-Manganese(III) 3-Meosalphen Complex. Journal of Structural Chemistry, 63, 1242-1255.
https://doi.org/10.1134/s0022476622080054
[16] Dou, L., Cai, J.Q., Feng, L.C., Dong, W.K. and Duan, J. (2022) Structure and Luminescence of Two Coordination Polymers with Nonsymmetrical Salamo-Based Ligand. Journal of Coordination Chemistry, 75, 1679-1690.
https://doi.org/10.1080/00958972.2022.2118053
[17] Dou, L., Hu, Z.F., Feng, L.C. and Dong, W.K. (2022) Differential Study on the Transition from a New Polyhalogen-Substituted Unsymmetric Salamo-Based Ligand to Its Cu(II) and Co(II) Complexes. Journal of Coordination Chemistry, 75, 2228-2244.
https://doi.org/10.1080/00958972.2022.2124509
[18] Li, X., Feng, S.S., Wei, Y.X. and Dong, W.K. (2022) An Investigation of a Relatively Rigid Acyclic Salamo-Type Ligand and Its Square Planar Cu(II) Complex. Journal of Coordination Chemistry, 75, 2245-2257.
https://doi.org/10.1080/00958972.2022.2123738
[19] Man, L.L., Tong, L., Gan, L.L., Li, R.Y., Mu, H.R. and Dong, W.K. (2022) A N2O2-Tetradentate Dioxime Fluorescence Probe for Highly Efficient Sensing of S2– and Solution Discoloration Detection of H2S Gas. Phosphorus, Sulfur, and Silicon and the Related Elements, 197, 1263-1272.
https://doi.org/10.1080/10426507.2022.2088758
[20] Man, L.L., Li, S.Z., Zhang, J., Zhang, Y. and Dong, W.K. (2023) A New Single-Armed Salamo-Based Sensor with Aggregation-Induced Emission Characteristic for Selective Sensing of Aluminium Ions. Journal of Photochemistry and Photobiology A: Chemistry, 437, Article ID: 114433.
https://doi.org/10.1016/j.jphotochem.2022.114433
[21] Huang, Y., Li, X., Li, W.D. and Dong, W.K. (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
[22] La, Y.T., Yan, Y.J., Gan, L.L., Xu, L. and Dong, W.K. (2023) Novel Phenoxo-Bridged Di-and Tri-Nuclear Cu(II) Salamo-Like Complexes Driven by Various Counter-Anions. Inorganica Chimica Acta, 546, Article ID: 121336.
https://doi.org/10.1016/j.ica.2022.121336
[23] Man, L.L., La, Y.T., Feng, L.C., Zhang, Y. and Dong, W.K. (2022) Investigation of Syntheses, Structures, Theoretical Calculations, and Fluorescence Properties of Two N3O-Donor Half-Salamo-Type Cu(II) Complexes. Journal of Coordination Chemistry, 76, 413-430.
[24] Guo, W.T., Ji, T.X., Deng, Y.H., Liu, J., Gou, Y.T. and Dong, W.K. (2022) Facile Synthesis of a Glutathione-Depleting Cu(II)-Half-Salamo-Based Coordination Polymer for Enhanced Chemodynamic Therapy. Dalton Transactions, 51, 11884-11891.
https://doi.org/10.1039/d2dt01786e
[25] Xie, K.F., Huang, Y., Li, S.Z., Li, L.L. and Dong, W.K. (2022) An Investigation into the Impact of Introduced Thiocyanate Anions on the Trinuclear Co(II) Salamo-Based Complex. Journal of Structural Chemistry, 63, 1262-1273.
https://doi.org/10.1134/s0022476622080078
[26] Ma, L.J., Li, X., Yan, Y.J., Yue, Y.N. and Dong, W.K. (2023) An Investigation of Two Heterobimetallic [Cu(II)2Ln(III)] (Ln = La and Ce) Complexes of a More Flexible Bis(Salamo)‐Type Ligand. Journal of Molecular Structure, 1275, Article ID: 134617.
https://doi.org/10.1016/j.molstruc.2022.134617
[27] Pu, L.M., Li, R.Y., Chen, Z.Z., Xu, W.B., Long, H.T. and Dong, W.K. (2022) An Aldehyde-Appended Salamo-Type Turn-On Optical Probe: Rapid Detection of Trace Cyanide Ions by Structural Conversion Program. Journal of Photochemistry and Photobiology A: Chemistry, 428, Article ID: 113883.
https://doi.org/10.1016/j.jphotochem.2022.113883
[28] Pu, L.M., Zhang, T., La, Y.T., Long, H.T., Xu, W.B. and Dong, W.K. (2022) A Study on Two Unusual Heterohexanuclear [CuII4LnIII2] (LnIII = LaIII and CeIII) Complexes with a N2O2-and O6-Donor Bis(Salamo)-Based Ligand. Inorganic Chemistry Communications, 146, Article ID: 110113.
https://doi.org/10.1016/j.inoche.2022.110113
[29] Peng, Y.D., Yan, Y.J., La, Y.T., Han, X.J., Huang, F. and Dong, W.K. (2022) Two Novel Cu(II) and Ni(II) Quinolone-Containing Half-Salamo-Like Complexes: Theoretical and Experimental Studies. Inorganic Chemistry Communications, 146, Article ID: 110121.
https://doi.org/10.1016/j.inoche.2022.110121
[30] Feng, T., Guo, S.Z., Li, M. and Zhao, L. (2022) A Insight into Structural Characterization, Hirshfeld Surface Analysis and DFT Theoretical Calculation of New Hexanuclear Ni(II) Complex Containing Two Different Coordination Modes of N3− Anions. Inorganic and Nano-Metal Chemistry, 54, 508-517.
https://doi.org/10.1080/24701556.2022.2034007
[31] Zhang, Y., Li, L.L., Huang, Y., Feng, T. and Dong, W.K. (2021) Investigations of New Five-Coordinate Dinuclear Co(II) and Cu(II) Salamo-Based Complexes. Journal of Coordination Chemistry, 74, 2912-2926.
https://doi.org/10.1080/00958972.2021.2018576
[32] Zhang, J.Q., Yao, G.X., Yan, Y.J., Xu, L., Zhang, Y. and Dong, W.K. (2022) Structurally Characterized Salamo-Based Mononuclear Cu(II) Complex Fluorogenic Sensor with High Selectivity for CN− and Cys-Cys. Journal of Molecular Structure, 1260, Article ID: 132772.
https://doi.org/10.1016/j.molstruc.2022.132772
[33] Han, X.J., Li, R.Y., Yue, Y.N., Zhang, Y. and Dong, W.K. (2022) Studying Anion-Dependent Paradoxically Fluorescent Cu(II) Complexes Bearing a Pyridine-Decorated Tetradentate Half-Salamo-Like Ligand. Inorganica Chimica Acta, 529, Article ID: 120634.
https://doi.org/10.1016/j.ica.2021.120634
[34] Hu, Z.F., Dou, L., Zhang, J., Zhang, Y., Sun, Y.X. and Dong, W.K. (2022) A Novel “On-Off-On” Halogen-Substituted Bis(Salamo)-Like Fluorogenic Chemosensor for Sequentially Identifying Cu2+ Ions and Cysteine. Inorganica Chimica Acta, 541, Article ID: 121090.
https://doi.org/10.1016/j.ica.2022.121090
[35] Huang, Y., Li, W.D., Wei, Y.X., Wang, L. and Dong, W.K. (2023) Structural, Theoretical and Optical Investigations of Two Lateral Twisting Trinuclear Co(II) and Ni(II) Salamo Type Complexes. Journal of Molecular Structure, 1272, Article ID: 134194.
https://doi.org/10.1016/j.molstruc.2022.134194
[36] Tong, L., Man, L.L., Li, X. and Dong, W.K. (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
[37] La, Y.T., Yan, Y.J., Li, X., Zhang, Y., Sun, Y.X. and Dong, W.K. (2023) Coordination-Driven Salamo-Salen-Salamo-Type Multinuclear Transition Metal(II) Complexes: Synthesis, Structure, Luminescence, Transformation of Configuration, and Nuclearity Induced by the Acetylacetone Anion. Inorganic Chemistry, 62, 9945-9963.
https://doi.org/10.1021/acs.inorgchem.3c01149
[38] Ma, C.Y., Li, X.X., Du, M.X., Dong, W.K. and Ding, Y.J. (2024) Deep Insights into Novel Hexa-Coordinated Phenoxy-Bridged Trinuclear Ni(II) Asymmetric Salamo-Like Complexes Affected by Different Types of Combined Solvents. Journal of Molecular Structure, 1298, Article ID: 137071.
https://doi.org/10.1016/j.molstruc.2023.137071
[39] Na, L.P., Li, X., Du, M.X., Zhang, Y. and Dong, W.K. (2023) A New Application of Salamo-Type Compounds: As a Photocatalyst of Designed Self-Assembling Cu(II) Dimer and Tetranuclear Co(II) Cuboidal Cluster. Journal of Molecular Structure, 1286, Article ID: 135594.
https://doi.org/10.1016/j.molstruc.2023.135594
[40] Niu, H.Y., Zheng, Y.R., Ding, Y.F., Wei, Y.X., Zhang, J., Guo, S.L., et al. (2023) The Unexpected Salamo-Type Copper(II) Complex: Synthesis, Structure, Theoretical Calculations and Fluorescence Properties. Journal of Molecular Structure, 1293, Article ID: 136250.
https://doi.org/10.1016/j.molstruc.2023.136250
[41] Tong, L., Gan, L.L., Zhang, H.W., Sun, Y.X., Niu, H.Y. and Dong, W.K. (2023) Synthesis, Structure, Theoretical Studies, and Properties of Dinuclear Cu(II) and Novel Trinuclear Co(II) Complexes with a More Flexible 3-Meosalamo-Like Ligand. Journal of Molecular Structure, 1294, Article ID: 136465.
https://doi.org/10.1016/j.molstruc.2023.136465
[42] Yan, Y.J., La, Y.T., Li, X., Zhang, Y., Dong, W.K. and Ding, Y.J. (2023) Investigating Poly-Nuclear Zn(II) and Ni(II) Complexes Based on a Formyl-Appended Single Salamo-Type Ligand. Journal of Molecular Structure, 1288, Article ID: 135843.
https://doi.org/10.1016/j.molstruc.2023.135843
[43] Zhang, J., Dou, L., Hu, Z.F. and Dong, W.K. (2023) The Investigation of Two Bis(Phenoxo)-Acetate-Bridged Binuclear Nickel(II) Complexes Driven by Different Alcohol Solvents. Journal of Coordination Chemistry, 76, 596-611.
https://doi.org/10.1080/00958972.2023.2201656
[44] Ding, Y.F., Man, L.L., Tong, L., Li, X., Dong, W.K. and Ding, Y.J. (2024) Differently Structural Cu(II) and Ni(II) Complexes of a Nonsymmetrical Tetradentate Half-Salamo Like N3O-Donor Ligand: Synthesis, Crystal Structure, Spectral Properties and Theoretical Studies. Journal of Molecular Structure, 1301, Article ID: 137341.
https://doi.org/10.1016/j.molstruc.2023.137341
[45] Du, M.X., Li, X.X., Ma, C.Y., Dong, W.K. and Ding, Y.J. (2024) A Unique N-Heterocyclic Oligo(N,O-Donor) Salamo-Ni(II)-Based Probe for Highly Selective Fluorescence Detection of Cr2O72-. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 310, Article ID: 123909.
https://doi.org/10.1016/j.saa.2024.123909
[46] Zhang, Y., Du, M.X., La, Y.T., Yan, Y.J. and Dong, W.K. (2024) Synthesis, Structural Characterizations and Theoretical Calculations of the Ni(II) Complex Based on a Novel Salamo-Salen-Salamo-Type Hybrid Ligand. Journal of Molecular Structure, 1296, Article ID: 136841.
https://doi.org/10.1016/j.molstruc.2023.136841
[47] Peng, Y.D., Huang, F., Du, M.X., La, Y.T., Yu, J., Hu, X. and Dong, W.K. (2024) Rare Formyl-Coordinated Homotrinuclear Copper(II) Salamo-Based N2O3-Donor Complex: Experimental and Theoretical Studies. Inorganica Chimica Acta, 560, Article ID: 121815.
https://doi.org/10.1016/j.ica.2023.121815
[48] Gan, L.L., Tong, L., Liu, L.L., Yue, Y.N. and Dong, W.K. (2024) Investigating Two Structurally Different Penta-Coordinated Trigonal Bipyramidal Co(II) Non-Symmetric Salamo-Type Complexes. Journal of Molecular Structure, 1296, Article ID: 136907.
https://doi.org/10.1016/j.molstruc.2023.136907
[49] Gan, L.L., Niu, H.Y., Liu, L.L., Dong, W.K. and Ding, Y.J. (2024) The Effect of Different Counter-Anions on Two Nonsymmetric Salamo-Type Copper(II) Complexes with Different Structures. Journal of Molecular Structure, 1302, Article ID: 137526.
https://doi.org/10.1016/j.molstruc.2024.137526
[50] Gan, L.L., Li, X., Du, M.X., Yan, Y.J., Zhang, Y., Dong, W.K. and Ding, Y.J. (2024) Study on Solvent Effect and Coordination Characteristics of Two Different Types of Cu(II) Salamo-Salen-Salamo-Hybrid Complexes. Journal of Molecular Structure, 1299, Article ID: 137199.
https://doi.org/10.1016/j.molstruc.2023.137199
[51] Yan, Y.B., Yang, R.W., Zhang, H.W., Zhang, Y. and Dong, W.K. (2024) Crystal Structure and Luminescent Mechanochromism of a Quinoline-Appended Acylhydrazone Ligand and Its Zn(II) Complex. Journal of Molecular Structure, 1299, Article ID: 137148.
https://doi.org/10.1016/j.molstruc.2023.137148