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Supramolecular poly{9-[4-(octyloxy)phenyl]fluoren-9-ol-2,7-diyl} (PPFOH)-based conjugated polymer sub-microspheres (CPSMs) with diameters ranging from 150 nm to several micrometres are constructed via “one step’ solvent evaporation induced interface self-assembly (SEIS). Their diameter and packing mode can be optimized by controlling the preparation parameters, which pave the way to construct colloidal crystal and light-emitting diodes.

One-step preparation of conjugated homopolymer sub-microspheres via a controllable supramolecular approach toward optoelectronic applications