Kirill Monakhov, Leibniz Institute of Surface Engineering (IOM), 04318 Leipzig, Germany. E-mail: kirill.monakhov@iom-leipzig.de
Abstract
Redox-active ligands, metal complexes, and larger coordination frameworks are chemically precise, responsive building blocks for smart materials, molecular electronics, energy storage, and neuromorphic device concepts. However, their redox behavior depends strongly on the experimental regime in which it is probed. Bulk electrochemistry, confined nanodroplet methods, electrochemical scanning probe microscopy, tunneling spectroscopy, and synchrotron-coupled nanospectroscopy often probe the same molecular event through fundamentally different physical observables. In this mini-review, we use polyoxometalates as a guiding molecular class to compare redox behavior across three length-scale regimes: bulk ensembles, confined nanoscale assemblies, and single-molecule or few-molecule junctions. We discuss cyclic voltammetry, scanning electrochemical probe methods, electrochemical scanning tunneling microscopy, scanning tunneling spectroscopy, electron-spin-resonance STM, scattering-type near-field optical microscopy, and synchrotron nanospectroscopic methods. We argue that advanced scanning probe microscopy provides the missing conceptual and experimental bridge between classical electrochemical redox potentials and nanoscale electronic charge and spin structure, enabling a regime-aware design language for redox-programmable molecular materials.
Keywords
References
-
1. Monakhov K, Petrovskii SK, Long DL, Nyman M, Kahnt A, Warneke J, et al. Polyoxometalates for health, electronics, energy, and the environment: Challenges, opportunities, and future horizons. ChemistryEurope. 2026;4(5):e70280.[DOI]
-
2. Ueda T. Electrochemistry of polyoxometalates: From fundamental aspects to applications. ChemElectroChem. 2018;5(6):823-838.[DOI]
-
3. Al-Shamery N, Lee PS, Unwin PR, Monakhov K. Redox-programmed surfaces via scanning electrochemical cell microscopy (SECCM). Trends Chem. 2025;7(9):494-496.[DOI]
-
4. Al-Shamery N, Valavanis D, Dean B, Dettlaff A, Sobaszek M, Bogdanowicz R, et al. Optimizing electrochemical microprinting of conducting polymers: Scanning electrochemical cell microscopy (SECCM) coupled with conveyor-belt surface analysis. Small Methods. 2026;10:e01781.[DOI]
-
7. Filoni C, Wandelt K, Marfori L, Leone M, Duò L, Ciccacci F, et al. A combined EC-STM and EC-AFM investigation of the sulfate adsorption on a Cu(111) electrode surface up to the anodic corrosion potential. Appl Surf Sci. 2023;611:155542.[DOI]
-
9. Hillenbrand R, Abate Y, Liu M, Chen X, Basov DN. Visible-to-THz near-field nanoscopy. Nat Rev Mater. 2025;10(4):285-310.[DOI]
-
11. Kim J, Kim JH, Ariga K. Redox-active polymers for energy storage nanoarchitectonics. Joule. 2017;1(4):739-768.[DOI]
-
12. Yamasaki N, Azuma SY, Hasegawa T, Ogo S, Ueda T. Voltammetric behaviour of Keggin-type copper-substituted tungstosulfate in acetonitrile: Electron transfer processes with deposition and stripping. J Electroanal Chem. 2026;1010:120036.[DOI]
-
14. Petrangolini P, Alessandrini A, Navacchia ML, Capobianco ML, Facci P. Electron transport properties of single-molecule-bearing multiple redox levels studied by EC-STM/STS. J Phys Chem C. 2011;115(40):19971-19978.[DOI]
-
15. Keat CJ. The new frontier of nanoengineering, an atomic-level blueprints for future devices. ISA. 2025;1(1):13-19.[DOI]
-
16. Benstetter G, Biberger R, Liu D. A review of advanced scanning probe microscope analysis of functional films and semiconductor devices. Thin Solid Films. 2009;517(17):5100-5105.[DOI]
-
17. Wu C, Qiao X, Robertson CM, Higgins SJ, Cai C, Nichols RJ, et al. A chemically soldered polyoxometalate single-molecule transistor. Angew Chem Int Ed. 2020;59(29):12029-12034.[DOI]
-
18. Zhao Q, Li B, Menon D, Zhu C, Alizadeh Kiapi MR, Chen X, et al. Cation-directed assembly and sequential functionalization enable superprotonic polyanion–organic frameworks for high-power fuel cells. Nat Chem. 2026;18(7):1231-1241.[DOI]
-
19. Monakhov K. Stimuli-responsive gold–polyoxometalate multielectron transformers. Inorg Chem Front. 2025;12(2):396-399.[DOI]
-
20. Salhi J, Mattera M, Arfaoui I, Calupitan JP, Alves S, Troufflard C, et al. Single polyoxometalate-based nanoclusters characterized by infrared absorption nanospectroscopy. Commun Chem. 2024;7:299.[DOI]
-
21. Moors M, Monakhov KY. Multistate switchable polyoxometalates as neuromimetic emulators. Mater Today. 2024;81:1-3.[DOI]
-
22. Glöβ M, Pütt R, Moors M, Kentzinger E, Pyckhout-Hintzen W, Monakhov KY. Interplay between the amphipathic polyoxometalate interactions in solution and at solid-liquid interfaces: A toolbox for the technical application. Nanoscale. 2019;11(10):4267-4277.
-
23. Chang S, Chen Y, Zhang J, Pan Q, Hua Y. Heterogeneous polyoxometalate-based catalysts for functionalized quinones synthesis: Systematic advances, prospects, and challenges. ChemPlusChem. 2025;90(8):e202500261.[DOI]
-
25. Yu SH, Hassan SZ, So C, Mingyun K, Chung DS. Molecular-switch-embedded solution-processed semiconductors. Adv Mater. 2023;35(4):2203401.[DOI]
-
26. Lanlan S, Diaz-Fernandez YA, Gschneidtner TA, Westerlund F, Lara-Avila S, Moth-Poulsen K. Single-molecule electronics: From chemical design to functional devices. Chem Soc Rev. 2014;43(21):7378-7411.[DOI]
-
27. Zhai Y, Zhu Z, Zhou S, Zhu C, Dong S. Recent advances in spectroelectrochemistry. Nanoscale. 2018;10(7):3089-3111.[DOI]
-
29. Torres D, Bailly J, Bernal M, Coelho LB, Ustarroz J. Electrochemical nucleation and the role of the surface state: Unraveling activity distributions with a cross-system examination and a local electrochemistry approach. J Solid State Electrochem. 2024;28(5):1719-1734.[DOI]
-
30. Martín-Yerga D, Unwin PR, Valavanis D, Xu X. Correlative co-located electrochemical multi-microscopy. Curr Opin Electrochem. 2023;42:101405.[DOI]
-
31. Ghoshal A, Kaur R, Sanku S, Singh AK, Mondal PC. A twist in the molecular memory function: Chemical compositions of different redox couples control the resistive switching bias polarity. J Mater Chem C. 2025;13(14):7307-7317.[DOI]
-
32. Sachan P, Mahapatra A, Sai Channapragada LA, Kaur R, Sahay S, Chandra Mondal P. Electrosynthesis of molecular memory elements. Chem Sci. 2025;16(24):10990-11001.[DOI]
-
34. Mini H, Park JE, Jo A. The meniscus in SECCM: Formation, stability, and its impact on quantitative electrochemistry. J Electrochem Sci Technol. 2026;17(3):304-320.[DOI]
-
36. Wang YQ, Wang D. Electrochemical scanning tunneling microscopy in electrocatalysis. Curr Opin Electrochem. 2024;46:101512.[DOI]
-
38. Cherevan AS, Nandan SP, Roger I, Rongji L, Streb C, Eder D. Polyoxometalates on functional substrates: Concepts, synergies, and future perspectives. Adv Sci. 2020;7(8):1903511.[DOI]
-
41. Huez C, Guérin D, Lenfant S, Volatron F, Calame M, Perrin ML, et al. Redox-controlled conductance of polyoxometalate molecular junctions. Nanoscale. 2022;14(37):13790-13800.[DOI]
-
43. Vogelsberg E, Moors M, Sorokina AS, Ryndyk DA, Schmitz S, Freitag JS, et al. Solution-processed formation of DNA-origami-supported polyoxometalate multi-level switches with countercation-controlled conductance tunability. Chem Mater. 2023;35(14):5447-5457.[DOI]
-
44. Phark SH, Weber B, Yoshida Y, Forrester PR, Elbertse RJG, Stroscio JA, et al. Roadmap on atomically-engineered quantum platforms. Nano Futur. 2025;9(3):032001.[DOI]
-
45. Choi DJ, Phark SH, Heinrich AJ, Lorente N. Electron spin resonance with scanning tunneling microscopy: A tool for an on-surface quantum platform of identical qubits. Nanoscale Adv. 2025;7(15):4551-4558.[DOI]
-
47. Bechtel HA, Muller EA, Olmon RL, Martin MC, Raschke MB. Ultrabroadband infrared nanospectroscopic imaging. Proc Natl Acad Sci U S A. 2014;111(20):7191-7196.[DOI]
-
48. Vicente RA, Raju SP, Gomes HVN, Neckel IT, Tolentino HCN, Fernández PS. Development of electrochemical cells and their application for spatially resolved analysis using a multitechnique approach: From conventional experiments to X-ray nanoprobe beamlines. Anal Chem. 2023;95(44):16144-16152.
-
49. Mino L, Borfecchia E, Segura-Ruiz J, Giannini C, Martinez-Criado G, Lamberti C. Materials characterization by synchrotron X-ray microprobes and nanoprobes. Rev Mod Phys. 2018;90(2):025007.[DOI]
-
50. Vicente RA, Neckel IT, Fernández PS. Mastering the use of nanoprobes beamlines for electrochemistry: The importance of tracking radiation damage and exploring material heterogeneity. ACS Electrochem. 2025;1(3):286-293.[DOI]
-
51. Hermann RJ, Gordon MJ. Nanoscale optical microscopy and spectroscopy using near-field probes. Annu Rev Chem Biomol Eng. 2018;9:365-387.[DOI]
-
52. Volatron F, Izzet G, Vuillaume D, Proust A. Unveiling polyoxometalate redox properties at the nanoscale. Comptes Rendus Chim. 2024;27(G1):255-268.[DOI]
-
53. Chen JJ, Vilà-Nadal L, Solé-Daura A, Chisholm G, Minato T, Busche C, et al. Effective storage of electrons in water by the formation of highly reduced polyoxometalate clusters. J Am Chem Soc. 2022;144(20):8951-8960.[DOI]
-
54. Guillén Soler M, Rauschen R, Laws K, Sharma A, Grocholski N, McNulty M, et al. ElectroChemputer with integrated monitoring for programmable electrochemistry. Chem. 2026;12(3):102907.[DOI]
-
55. Willke P, Bilgeri T, Zhang X, Wang Y, Wolf C, Aubin H, et al. CoherentSpin control of single molecules on a surface. ACS Nano. 2021;15(11):17959-17965.[DOI]
-
56. Sellies L, Repp J. Electron spin resonance at the single-molecule scale. Angew Chem Int Ed. 2025;64(37):e202506539.[DOI]
-
57. Wiens R, Findlay CR, Baldwin SG, Kreplak L, Lee JM, Veres SP, et al. High spatial resolution (1.1 μm and 20 nm) FTIR polarization contrast imaging reveals pre-rupture disorder in damaged tendon. Faraday Discuss. 2016;187:555-573.[DOI]
-
58. Ai F, Lu YC. Coordination chemistry in advanced redox-active electrolyte designs. Nat Rev Mater. 2025;10(12):929-946.[DOI]
-
59. Hörner G, Weber B. Switching spin-states: Spin crossover vs. Coordination-induced spin-state switching. Eur J Inorg Chem. 2024;27(35):e202400471.[DOI]
-
60. Saygili Y, Stojanovic M, Flores-Díaz N, Zakeeruddin SM, Vlachopoulos N, Grätzel M, et al. Metal coordination complexes as redox mediators in regenerative dye-sensitized solar cells. Inorganics. 2019;7(3):30.[DOI]
-
62. Bertini I, Luchinat C, Parigi G, Ravera E. Transition metal ions: Shift and relaxation. In: Solution NMR of paramagnetic molecules. Amsterdam: Elsevier; 2017. p. 175-253.[DOI]
-
64. Zhang Y, Torres-Cavanillas R, Yan X, Zeng Y, Jiang M, Clemente-León M, et al. Spin crossover iron complexes with spin transition near room temperature based on nitrogen ligands containing aromatic rings: From molecular design to functional devices. Chem Soc Rev. 2024;53(17):8764-8789.
-
66. Das A, Yufeng R, Hessin C, Desage-El Murr M. Copper catalysis with redox-active ligands. Beilstein J Org Chem. 2020;16:858-870.[DOI]
-
69. Tahoun M, Gee CT, McCoy VE, Sander PM, Müller CE. Chemistry of porphyrins in fossil plants and animals. RSC Adv. 2021;11(13):7552-7563.[DOI]
-
73. Gray HB, Winkler JR. Electron transfer in proteins. Annu Rev Biochem. 1996;65:537-561.[DOI]
-
74. Cojocariu I, Carlotto S, Zamborlini G, Jugovac M, Schio L, Floreano L, et al. Reversible redox reactions in metal-supported porphyrin: The role of spin and oxidation state. J Mater Chem C. 2021;9(37):12559-12565.[DOI]
-
75. Zhang Y, Si W, Hou X, Gao Q, Zhao C, Liang R, et al. Single-molecule spin devices: Fundamentals, advances, and prospects. Nano Res. 2026;19(6):94908552.[DOI]
-
77. Anjass M, Lowe GA, Streb C. Molecular vanadium oxides for energy conversion and energy storage: Current trends and emerging opportunities. Angew Chem Int Ed. 2021;60(14):7522-7532.[DOI]
-
78. Arya N, Philipp T, Greiner S, Steiner M, Kranz C, Anjass M. Reversible electrodeposition of potassium-bridged molecular vanadium oxides: A new approach towards multi-electron storage. Angew Chem Int Ed. 2023;62(35):e202306170.[DOI]
Copyright
© The Author(s) 2027. This is an Open Access article licensed under a Creative Commons Attribution 4.0 International License (https://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, sharing, adaptation, distribution and reproduction in any medium or format, for any purpose, even commercially, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.
Publisher’s Note
Share And Cite


