Toward advanced functional systems: Honeycomb-like polymeric surfaces incorporating polyoxovanadates with surface-appended copper-cyclam complexes

In this work the immobilization of hybrid polyoxometalates (POMs) onto functional polymeric surfaces is exposed and discussed. Thus, various hybrid polymer-inorganic films were prepared by anchoring selected hybrid POMs onto tailored polymeric surfaces that consisted of breath figures (BFs) made of polystyrene-b-poly(acrylic acid)/polystyrene (PS-b-PAA/PS) blends. Functionalization of the BF films was performed by selective arrangement of acrylic acid groups of the amphiphilic block copolymer on the surface pores because of their affinition for the water condensed during breath figure formation. These carboxylic acid functional groups contained within the PAA blocks were then employed to anchor [Cu(cyclam)][{Cu(cyclam)}₂(V₁₀O₂₈)]·10H2O (1-CuV10) and [{Cu(cyclam)}(VO₃)₂]·5H₂O (1-CuV1), hybrid POMs by immersing the films into aqueous solutions of the in situ formed hybrid clusters, resulting in the hybrid films BF1 and BF2, respectively. Superficial analysis of these hybrid polymeric films was carried out by the sophisticated ion beam-based technique time-of-flight secondary ion mass spectrometry (ToF-SIMS) that was revealed to be an excellent method for the superficial compositional mapping of patterned surfaces.