Chromophores bound to nanostructured, wide band gap metal oxide semiconductors are used in sensing devices as well as in photo-catalysis, photovoltaics, and photo-degradation of chemicals.  ZnO exhibits high electron mobility, piezoelectricity, and can be grown as highly crystalline, vertically aligned nanowires, an ordered morphology that is advantageous in many electronic applications.  Standard methods of metal oxide surface modification with chromophoric molecules involve the liquid phase reaction with a carboxylic anchor group derivative, however in these conditions ZnO is etched by the acidic anchor groups. The etching of the ZnO surface results in the formation of zincate salts and poor predictability of the surface species produced, which may prevent many applications and provide erroneous results in heterogeneous electron transfer (HET) studies. Here we demonstrate a two-step functionalization process where, in the first step, the solution-grown ZnO nanorods surface is functionalized and passivated by chemisorption of propiolic acid (2-propynoic acid) from gas phase through the COOH group, and forming an ethyne-functionalized monolayer ready for click chemistry. The subsequent ethyne-azide click reaction with a perylene-azide derivative in liquid phase, resulted in a highly ordered chromophore/ZnO interface which fully preserved the integrity of the ZnO nanorod structure.  The perylene polyaromatic hydrocarbon framework was selected for ongoing HET studies due to its favorable photophysical properties, and this poster will describe our progress in the synthesis of a variety of novel perylene derivatives developed for this purpose.<br/>

Morphology-preserving sensitization of ZnO nanoparticle surfaces with perylene chromophores via click-chemistry

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.