双齿膦、巯基与无机离子共配的Ag基纳米团簇的研究进展
Research Progress of Ag-Based Nanoclusters with Bidentate Phosphine, Thiol and Inorganic Ions
DOI: 10.12677/ms.2026.165122, PDF,   
作者: 杨青红：武汉工程大学化学与环境工程学院，湖北 武汉
关键词: Ag基纳米团簇；双齿膦配体；巯基配体；无机离子；Silver-Based Nanoclusters； Bidentate Phosphine Ligands； Thiol Ligands； Inorganic Ion
摘要: 原子精确的银基纳米团簇因其独特的量子尺寸效应、可调的电子结构与丰富的物理化学性能，成为纳米材料与配位化学领域的研究前沿。双齿膦配体、巯基配体与无机离子的多元共配策略，通过协同配位效应，为银纳米团簇的结构精准调控、稳定性提升及功能拓展提供了全新路径。本文系统综述该类共配银基纳米团簇的研究进展，并对该领域未来的挑战与发展方向进行展望。
Abstract: Atomically precise silver-based nanoclusters have become the research frontier in the field of nanomaterials and coordination chemistry due to their unique quantum size effect, adjustable electronic structure and rich physical and chemical properties. The multi-coordination strategy of bidentate phosphine ligands, thiol ligands and inorganic ions provides a new path for the precise regulation of the structure, stability improvement and functional expansion of silver nanoclusters through the synergistic coordination effect. In this paper, the research progress of this kind of co-assigned silver-based nanoclusters is systematically reviewed, and the future challenges and development directions in this field are prospected.
文章引用：杨青红. 双齿膦、巯基与无机离子共配的Ag基纳米团簇的研究进展[J]. 材料科学, 2026, 16(5): 288-299. https://doi.org/10.12677/ms.2026.165122

参考文献

[1] Yao, Q., Zhu, M., Yang, Z., Song, X., Yuan, X., Zhang, Z., et al. (2024) Molecule-Like Synthesis of Ligand-Protected Metal Nanoclusters. Nature Reviews Materials, 10, 89-108. [Google Scholar] [CrossRef] 
[2] Matus, M.F. and Häkkinen, H. (2023) Understanding Ligand-Protected Noble Metal Nanoclusters at Work. Nature Reviews Materials, 8, 372-389. [Google Scholar] [CrossRef] 
[3] Goswami, T., Bheemaraju, A., Sharma, A.K. and Bhandari, S. (2021) Perylenetetracarboxylic Acid-Incorporated Silver Nanocluster for Cost-Effective Visible-Light-Driven Photocatalysis and Catalytic Reduction. Colloid and Polymer Science, 299, 925-936. [Google Scholar] [CrossRef] 
[4] Gonzàlez-Rosell, A. and Copp, S.M. (2024) An Atom-Precise Understanding of DNA-Stabilized Silver Nanoclusters. Accounts of Chemical Research, 57, 2117-2129. [Google Scholar] [CrossRef] [PubMed]
[5] Ding, X., Zhang, C., Shi, L., Wang, J., Yang, X., Zhang, L., et al. (2024) Synergistic Coordination of Diphosphine with Primary and Tertiary Phosphorus Centers: Ultrastable Icosidodecahedral Ag30 Nanoclusters with Metallic Aromaticity. Science Advances, 10, eads0728. [Google Scholar] [CrossRef] [PubMed]
[6] Zhang, S., Liu, R., Zhang, X., Feng, L., Xue, Q., Gao, Z., et al. (2021) Core Engineering of Paired Core-Shell Silver Nanoclusters. Science China Chemistry, 64, 2118-2124. [Google Scholar] [CrossRef] 
[7] Xu, C., Yuan, Q., Wei, X., Li, H., Shen, H., Kang, X., et al. (2022) Surface Environment Complication Makes Ag29 Nanoclusters More Robust and Leads to Their Unique Packing in the Supracrystal Lattice. Chemical Science, 13, 1382-1389. [Google Scholar] [CrossRef] [PubMed]
[8] Anson, C.E., Eichhöfer, A., Issac, I., Fenske, D., Fuhr, O., Sevillano, P., et al. (2008) Synthesis and Crystal Structures of the Ligand‐Stabilized Silver Chalcogenide Clusters [Ag154Se77(dppxy)18], [Ag320(StBu)60S130(dppp)12], [Ag352S128(StC5H11)96], and [Ag490S188(StC5H11)114]. Angewandte Chemie International Edition, 47, 1326-1331. [Google Scholar] [CrossRef] [PubMed]
[9] Zhang, S., Alkan, F., Su, H., Aikens, C.M., Tung, C. and Sun, D. (2019) [Ag48(C≡CtBu)20(CrO4)7]: An Atomically Precise Silver Nanocluster Co-Protected by Inorganic and Organic Ligands. Journal of the American Chemical Society, 141, 4460-4467. [Google Scholar] [CrossRef] [PubMed]
[10] Wang, Q., Lin, Y. and Liu, K. (2015) Role of Anions Associated with the Formation and Properties of Silver Clusters. Accounts of Chemical Research, 48, 1570-1579. [Google Scholar] [CrossRef] [PubMed]
[11] Villalba, F. and Albéniz, A.C. (2025) Understanding the Ligand Influence in the Multistep Reaction of Diazoalkanes with Palladium Complexes Leading to Carbene-Aryl Coupling. Organometallics, 44, 394-402. [Google Scholar] [CrossRef] [PubMed]
[12] Hilliard, J.S., Murray, D.J., Saha, A., Goldberger, J.E. and Wade, C.R. (2025) MoF-Supported Diphosphine Ligands for Iridium-Catalyzed C-H Borylation of Arenes. Inorganic Chemistry, 64, 7127-7136. [Google Scholar] [CrossRef] [PubMed]
[13] Bhowmik, M.L., Al Mamun, M.A., Nesterov, V.N., Sarker, J.C., Kabir, S.E. and Hogarth, G. (2025) Cyclic Metallophosphines via an Unexpected Series of Metal-Mediated P-C and C-C Bond Rearrangements. Inorganic Chemistry, 64, 19520-19524. [Google Scholar] [CrossRef] 
[14] Beliaeva, M., Belyaev, A., Korhonen, H., Mrózek, O., Jänis, J., Steffen, A., et al. (2026) Acid-Base Interactions in Luminescent Silver(I) and Gold(I) Complexes with Phosphine-Phosphinate/Phosphinite Ligands. Inorganic Chemistry Frontiers, 13, 511-524. [Google Scholar] [CrossRef] 
[15] Zhang, S., Li, H., Appel, A.M., Hall, M.B. and Bullock, R.M. (2020) Controlling P-C/C-H Bond Cleavage in Nickel Bis(diphosphine) Complexes: Reactivity Scope, Mechanism, and Computations. Organometallics, 39, 3306-3314. [Google Scholar] [CrossRef] 
[16] Fei, W., Tao, Y., Qiao, Y., Tang, S.Y. and Li, M.B. (2023) Structural Modification and Performance Regulation of Atomically Precise Metal Nanoclusters by Phosphine. Polyoxometalates, 2, Article 9140043. [Google Scholar] [CrossRef] 
[17] Duan, G., Han, J., Yang, B., Xie, Y. and Lu, X. (2020) Oxometalate and Phosphine Ligand Co-Protected Silver Nanoclusters: Ag28(dppb)6(MO4)4 and Ag32(dppb)12(MO4)4(NO3)4. Nanoscale, 12, 1617-1622. [Google Scholar] [CrossRef] [PubMed]
[18] Marchioni, M., Battocchio, C., Joly, Y., Gateau, C., Nappini, S., Pis, I., et al. (2020) Thiolate-Capped Silver Nanoparticles: Discerning Direct Grafting from Sulfidation at the Metal-Ligand Interface by Interrogating the Sulfur Atom. The Journal of Physical Chemistry C, 124, 13467-13478. [Google Scholar] [CrossRef] 
[19] Tian, Z., Song, C., Wang, C., Xu, H. and Guan, Q. (2020) Structures and Properties of [Ag(Ag2S)n]+ Clusters with N = 1-9: A Density Functional Theory Study. Journal of Nanoparticle Research, 22, Article No. 161. [Google Scholar] [CrossRef] 
[20] Ma, Z., Ren, Z., Dong, X. and Pan, F. (2025) Thiolated Disc Nanoclusters with Pseudo-6-Fold Symmetry. Inorganic Chemistry, 64, 11370-11379. [Google Scholar] [CrossRef] [PubMed]
[21] Huang, R., Dong, X., Yan, B., Du, X., Wei, D., Zang, S., et al. (2018) Tandem Silver Cluster Isomerism and Mixed Linkers to Modulate the Photoluminescence of Cluster‐Assembled Materials. Angewandte Chemie International Edition, 57, 8560-8566. [Google Scholar] [CrossRef] [PubMed]
[22] Biswas, S., Das, S. and Negishi, Y. (2023) Progress and Prospects in the Design of Functional Atomically-Precise Ag(I)-Thiolate Nanoclusters and Their Assembly Approaches. Coordination Chemistry Reviews, 492, 215255. [Google Scholar] [CrossRef] 
[23] Wang, Y. and Bürgi, T. (2021) Ligand Exchange Reactions on Thiolate-Protected Gold Nanoclusters. Nanoscale Advances, 3, 2710-2727. [Google Scholar] [CrossRef] [PubMed]
[24] Chen, Y., Bian, G., Wu, Z. and Tang, Q. (2025) Revealing the Exchange Kinetics of Thiol-Capped Au25 Nanoclusters with Alkynyl Ligands. Chemical Science, 16, 18748-18765. [Google Scholar] [CrossRef] 
[25] Kumar, P., Khirid, S., Jangid, D.K., Nishad, C.S., Chauhan, P., Kumari, P., et al. (2024) Dithiophosphonate-Protected Eight-Electron Superatomic Ag21 Nanocluster: Synthesis, Isomerism, Luminescence, and Catalytic Activity. Inorganic Chemistry, 63, 13724-13737. [Google Scholar] [CrossRef] [PubMed]
[26] Horita, Y., Ishimi, M. and Negishi, Y. (2023) Anion-Templated Silver Nanoclusters: Precise Synthesis and Geometric Structure. Science and Technology of Advanced Materials, 24, Article ID: 2203832. [Google Scholar] [CrossRef] [PubMed]
[27] Bowmaker, G.A., Effendy, Nitiatmodjo, M., Skelton, B.W. and White, A.H. (2005) Syntheses and Structures of Some Adducts of Silver(I) Oxyanion Salts with Some 2-N,O-Donor-Substituted Pyridine Bases. Inorganica Chimica Acta, 358, 4327-4341. [Google Scholar] [CrossRef] 
[28] Ge, R., Li, X. and Zheng, S. (2021) Recent Advances in Polyoxometalate-Templated High-Nuclear Silver Clusters. Coordination Chemistry Reviews, 435, Article ID: 213787. [Google Scholar] [CrossRef] 
[29] Li, Y., Liu, Z., Liu, W., Yuan, Z., Yang, P., Xu, J., et al. (2025) Halide‐Directed Ligand Engineering Enables Expedient, Controlled and Divergent Syntheses of Diphosphine‐Protected Au Nanoclusters. Small, 21, Article ID: 2500189. [Google Scholar] [CrossRef] [PubMed]
[30] Du, Y., Sheng, H., Astruc, D. and Zhu, M. (2019) Atomically Precise Noble Metal Nanoclusters as Efficient Catalysts: A Bridge between Structure and Properties. Chemical Reviews, 120, 526-622. [Google Scholar] [CrossRef] [PubMed]
[31] Shen, Y., Zhao, P., Jin, J., Han, J., Liu, C., Liu, Z., et al. (2021) A Comparative Study of [Ag11(iPrS)9(dppb)3]2+ and [Ag15S(sBuS)12(dppb)3]+: Templating Effect on Structure and Photoluminescence. Dalton Transactions, 50, 10561-10566. [Google Scholar] [CrossRef] [PubMed]
[32] Xia, Y., Fang, J., Xia, X., Liu, Z., Xie, Y. and Lu, X. (2022) Silver Clusters Coprotected by Different Diphosphine and Thiol Ligands. Crystal Growth & Design, 22, 5658-5665. [Google Scholar] [CrossRef] 
[33] Zhou, M., Li, K., Pei, Y., Jin, S. and Zhu, M. (2023) Effect of Specific Heavy Doping of Silver Atoms into the Icosahedral Au13 on Electronic Structure and Catalytic Performance. The Journal of Physical Chemistry Letters, 14, 11715-11724. [Google Scholar] [CrossRef] [PubMed]
[34] Ma, A., Li, Y., Zuo, Y., Zhang, S., Wang, Y., Ren, Y., et al. (2025) Atomic‐Level Insights into the Synergistic Effect between Ligands on Electrochemical CO2 Reduction: Based on Au7 Ag8 Series Nanoclusters. Rare Metals, 44, 4691-4700. [Google Scholar] [CrossRef] 
[35] Wang, S., Tan, Y., Li, T., Zhou, Q., Li, P., Yang, S., et al. (2022) Insight into the Role of Copper in the Transformation of a [Ag25(2,5-DMBT)16(DPPF)3]+ Nanocluster: Doping or Oxidation. Inorganic Chemistry, 61, 18450-18457. [Google Scholar] [CrossRef] [PubMed]
[36] Zhang, W., Liu, Z., Song, K., Aikens, C.M., Zhang, S., Wang, Z., et al. (2020) A 34‐Electron Superatom Ag78 Cluster with Regioselective Ternary Ligands Shells and Its 2D Rhombic Superlattice Assembly. Angewandte Chemie International Edition, 60, 4231-4237. [Google Scholar] [CrossRef] [PubMed]
[37] Jing, M., Kuang, K., Fang, C., Zhou, C., Li, Z., Chen, S., et al. (2024) Structure‐Dependent Photoluminescence and Chemiluminescence Emission Enhancement in Ag25 Nanoclusters. Advanced Optical Materials, 12, Article ID: 2400940. [Google Scholar] [CrossRef] 
[38] Liu, J., Fang, C., Kuang, K., Zhou, C., Li, Z., Ma, W., et al. (2025) Anions-and Solvents-Triggered Reversible Interconversion in Silver Nanocluster and Their Assembly. Inorganic Chemistry, 64, 23157-23165. [Google Scholar] [CrossRef] 
[39] Bestgen, S., Fuhr, O., Breitung, B., Kiran Chakravadhanula, V.S., Guthausen, G., Hennrich, F., Yu, W., et al. (2017) [Ag115S34(SCH2C6H4tBu)47(dpph)6]: Synthesis, Crystal Structure and NMR Investigations of a Soluble Silver Chalcogenide Nanocluster. Chemical Science, 8, 2235-2240. [Google Scholar] [CrossRef] [PubMed]
[40] Ma, X., He, S., Li, Q., Li, Q., Chai, J., Ma, W., et al. (2023) Motif-to-Core Nucleation in a Decahedral Evolution Pattern. Inorganic Chemistry, 62, 15680-15687. [Google Scholar] [CrossRef] [PubMed]
[41] Li, X., Su, H., Zhou, R., Feng, S., Tan, Y., Wang, X., et al. (2016) General Assembly of Twisted Trigonal‐Prismatic Nonanuclear Silver(I) Clusters. Chemistry—A European Journal, 22, 3019-3028. [Google Scholar] [CrossRef] [PubMed]
[42] Liang, X., Li, Y., Wang, Z., Zhang, S., Liu, Y., Cao, Z., et al. (2021) Revealing the Chirality Origin and Homochirality Crystallization of Ag14 Nanocluster at the Molecular Level. Nature Communications, 12, Article No. 4966. [Google Scholar] [CrossRef] [PubMed]
[43] Zou, X., Jin, S., Du, W., Li, Y., Li, P., Wang, S., et al. (2017) Multi-Ligand-Directed Synthesis of Chiral Silver Nanoclusters. Nanoscale, 9, 16800-16805. [Google Scholar] [CrossRef] [PubMed]
[44] Zou, X., Jin, S., Wei, X., Li, X., Zhou, M., Wang, S., et al. (2020) Overall Structures of Two Metal Nanoclusters: Chloride as a Bridge Fills the Space between the Metal Core and the Metal Shell. Inorganic Chemistry, 59, 11905-11909. [Google Scholar] [CrossRef] [PubMed]
[45] Zhou, C., Pan, P., Wei, X., Lin, Z., Chen, C., Kang, X., et al. (2022) Horizontal Expansion of Biicosahedral M13-Based Nanoclusters: Resolving Decades-Long Questions. Nanoscale Horizons, 7, 1397-1403. [Google Scholar] [CrossRef] [PubMed]
[46] Zhou, M., Li, K., Wang, P., Zhou, H., Jin, S., Pei, Y., et al. (2023) Overall Structure of Au12Ag60(S-c-C6H11)31Br9(dppp)6: Achieving a Stronger Assembly of Icosahedral M13 Units. Nanoscale, 15, 2633-2641. [Google Scholar] [CrossRef] [PubMed]
[47] Deng, H., Li, X., Yan, X., Jin, S., et al. (2022) Regulation of Surface Structure of [Au9Ag12(SAdm)4(Dppm)6Cl6](SbF6)3 Nanocluster via Alloying. Frontiers in Chemistry, 9, Article 793339. [Google Scholar] [CrossRef] [PubMed]
[48] Li, X., Wang, Z., Su, H., Feng, S., Kurmoo, M., Tung, C., et al. (2017) Anion-Templated Nanosized Silver Clusters Protected by Mixed Thiolate and Diphosphine. Nanoscale, 9, 3601-3608. [Google Scholar] [CrossRef] [PubMed]
[49] Khatun, E., Bodiuzzaman, M., Sugi, K.S., Chakraborty, P., Paramasivam, G., Dar, W.A., et al. (2019) Confining an Ag10 Core in an Ag12 Shell: A Four-Electron Superatom with Enhanced Photoluminescence upon Crystallization. ACS Nano, 13, 5753-5759. [Google Scholar] [CrossRef] [PubMed]
[50] Wang, Y., Xiong, L., Cheng, Q., Hu, D., Jin, S. and Zhu, M. (2025) Structural Disproportionation of Ag20Cu10 Highlights the Impact of Cluster Structure on Electrocatalytic Properties for CO2 Reduction. Inorganic Chemistry Frontiers, 12, 2495-2505. [Google Scholar] [CrossRef] 
[51] Deng, G., Yoo, S., Liu, X., Shim, J., Bootharaju, M.S. and Hyeon, T. (2025) Atomically Precise Ag26 Nanocluster with a Layered Core: Synthesis, Total Structure and Photocatalysis. Nano Research, 18, Article ID: 94907950. [Google Scholar] [CrossRef] 

为你推荐