Mechanical control of molecular aggregation and fluorescence switching/enhancement in an ultrathin film

Optical responses of molecular aggregates and assemblies are often different from that of the individual molecules. Self-assembly approaches provide little physical control on the extent of aggregation. Mechanical compression of amphiphilic molecules (with chromophore/fluorophore head groups) at the air-water interface, followed by transfer as Langmuir-Blodgett (LB) films, should prove to be an elegant route to molecular assemblies with systematically tunable aggregation and optical responses. This concept is demonstrated using monolayer LB films of a diaminodicyanoquinodimethane (DADQ)-based amphiphile fabricated at different surface pressures. Films deposited above a threshold pressure exhibit a strong blue-shift in the absorption and fluorescence relative to those deposited below; computational investigations suggest that this is due to the formation of 2-dimensional close-packed assemblies. Significantly, the blue emission of the films deposited above the threshold pressure increases with compaction, demonstrating aggregation-induced fluorescence enhancement in ultrathin films, a phenomenon well-established in crystals and nanocrystals of selected classes of molecules including the DADQs. The sharp contrast with aggregation-induced fluorescence quenching observed with most dye molecules is illustrated by a parallel investigation of LB films of a hemicyanine-based amphiphile. The present study illustrates the efficacy of simple mechanical compression and the LB technique in fabricating ultrathin films with tailored supramolecular assembly and optical responses.