Integration of Redox-Active Polyoxovanadate Clusters into PMMA: Structure, Nanoscale Organization and Multilevel Redox Switching

Abstract

Developing electrically contacted architectures for molecular data storage remains a central challenge in molecular electronics. Here, we integrate redox-active polyoxovanadate clusters – [V₆O₁₃((OCH₂)₃CCH₂OH)₂]^2– charge-balanced by nBu₄N⁺ (TBA-V₆OH) – into a solvent-processable poly(methyl methacrylate) (PMMA) matrix and investigate their structural and electronic behavior as a function of composition and processing. Spectroscopic and microscopic analyses confirm preservation of the polyoxometalate framework and reveal concentration-dependent organization from isolated species to extended domains. Scanning tunneling microscopy/spectroscopy (STM/STS) demonstrates redox-dependent switching at the nanoscale, which remains observable across different morphologies. Macroscopic electrical measurements on prototype devices further indicate that this redox activity is retained in an electrically contacted configuration. These results establish a processable POM–polymer composite platform for exploring redox-active molecular functionality in solid-state environments.