Morphologically Diverse Micro- and Macrostructures Created via Solvent Evaporation-Induced Assembly of Fluorescent Spherical Particles in the Presence of Polyethylene Glycol Derivatives

The creation of fluorescent micro- and macrostructures with the desired morphologies and sizes is of considerable importance due to their intrinsic functions and performance. However, it is still challenging to modulate the morphology of fluorescent organic materials and to obtain insight into the factors governing the morphological evolution. We present a facile bottom-up approach to constructing diverse micro- and macrostructures by connecting fluorescent spherical particles (SPs), which are generated via the spherical assembly of photoisomerizable azobenzene-based propeller-shaped chromophores, only with the help of commercially available polyethylene glycol (PEG) derivatives. Without any extra additives, solvent evaporation created a slow morphological evolution of the SPs from short linear chains (with a length of a few micrometers) to larger, interconnected networks and sheet structures (ranging from tens to >100 µm) at the air–liquid interface. Their morphologies and sizes were significantly dependent on the fraction and length of the PEG. Our experimental results suggest that noncovalent interactions (such as hydrophobic forces and hydrogen bonding) between the amphiphilic PEG chains and the relatively hydrophobic SPs were weak in aqueous solutions, but play a crucial role in creating the morphologically diverse micro- and macrostructures. Moreover, short-term irradiation with visible light caused fast morphological crumpling and fluorescence switching of the obtained structures.