From Solid-State Cluster Compounds to Functional PMMA-Based Composites with UV and NIR Blocking Properties, and Tuned...

New nanocomposite materials with UV-NIR blocking properties and hues ranging from green to brown were prepared by integrating inorganic tantalum octahedral cluster building blocks prepared via solid-state chemistry in a PMMA matrix. After the synthesis by the solid-state chemical reaction of the K₄[{Ta₆Brⁱ₁₂}Br^a₆] ternary halide, built-up from [{Ta₆Brⁱ₁₂}Br^a₆]^4- anionic building blocks, and potassium cations, the potassium cations were replaced by functional organic cations (Kat⁺) bearing a methacrylate function. The resulting intermediate, (Kat)₂[{Ta₆Brⁱ₁₂}Br^a₆], was then incorporated homogeneously by copolymerization with MMA into transparent PMMA matrices to form a brown transparent hybrid composite Ta@PMMA_brown. The color of the composites was tuned by controlling the charge and consequently the oxidation state of the cluster building block. Ta@PMMA_green was obtained through the two-electron reduction of the [{Ta₆Brⁱ₁₂}Br^a₆]^2- building blocks from Ta@PMMA_brown in solution. Indeed, the control of the oxidation state of the Ta₆ cluster inorganic building blocks occurred inside the copolymer, which not only allowed the tuning of the optical properties of the composite in the visible region but also allowed the tuning of its UV and NIR blocking properties.