Tuning Microstructures in Organogels: Gelation and Spectroscopic Properties of Mono- and Bis-cholesterol-Linked Diphenylbutadiene Derivatives

The gelation and photophysical properties of mono- and bis-cholesterol derivatives linked to diphenylbutadiene have been investigated. Scanning electron microscopy of xerogels of the monocholesterol derivatives indicated that these molecules self-assemble into 3D networks consisting of helically twisted fibers. In contrast, the morphology of xerogels of the bis-cholesterol derivatives indicated agglomerated spheres. In concentrated solutions (> 10(-4) M), the self-assembled superstructure of the monocholesterol derivatives consists of helically twisted fibers whereas that of the bis-cholesterol derivatives indicated clustered spheres. An investigation of spectroscopic properties suggests that the morphology of the superstructures formed in these systems may be correlated to the nature of the molecular aggregates formed. Absorption and emission spectral studies as a function of concentration and temperature suggested the formation of predominantly J-type aggregates in the monocholesterol and H-type aggregates in the bis-cholesterol derivatives. It is proposed that the slipped slack arrangement within the J aggregates of the monocholesterol derivatives resulted in the formation of helically twisted fibers, whereas the cofacial arrangement in the H aggregates of the bis-cholesterol derivatives could prevent such fiber formation, resulting in the formation of the agglomerated spheres.