Light-Induced and Thermal Isomerization of Azobenzenes on Immobilized Gold Nanoparticle Aggregates.

Morphologically different gold nanoparticle (AuNP) aggregates were prepared on macroscopic surfaces covered with a layer of polydopamine (PDA). The extent of particle aggregation and the particle size distribution could be controlled by the Au(III) reduction times, while the reduction process was triggered solely by the redox active polymer. Shorter reaction times led to smaller particles along with lower levels of aggregation, while longer reductions resulted in larger average particle diameter and heavier aggregation. The prepared surfaces were characterized by UV-Vis, AFM and KPFM techniques. These surfaces were used as solvent-free condensed phases to probe the photochemical and thermal isomerization processes of attached azobenzenes with different spacer lengths. Fast and reversible light-induced switching was observed in each case. The thermal cis-to-trans isomerization was found to be accelerated for particle-bound azobenzenes compared to those in solution.