Continuous and Segmented Semiconducting Fiber-like Nanostructures with Spatially Selective Functionalization by Living Crystallization-driven Self-assembly.

Fiber-like π-conjugated nanostructures are important components of flexible organic electronic and optoelectronic devices. To broaden the range of potential applications, one needs to control not only the length of these nanostructures, but the introduction of diverse functionality with spatially selective control. Here we report the synthesis of a crystalline-coil block copolymer of oligo( p -phenylenevinylene)- b -poly(2-vinylpyridine) (OPV 5 - b -P2VP 44 , the subscripts represent the mean number of repeat units of each block), in which the basicity and coordinating/chelating ability of the P2VP segment provide a landscape for the incorporation of a variety of functional inorganic NPs. Through a self-seeding strategy, we were able to prepare monodisperse fiber-like micelles of OPV 5 - b -P2VP 44 with lengths ranging from 50 to 800 nm. Significantly, the exposed two ends of OPV core of these fiber-like micelles remained active toward further epitaxial deposition of OPV 5 - b -PNIPAM 49 (PNIPAM = poly( N -isopropylacrylamide)) and OPV 5 - b -P2VP 44 to generate uniform A-B-A and B-A-B-A-B segmented block comicelles with tunable lengths for each block. The P2VP domains in these (co-)micelles can be selectively decorated with diverse inorganic and polymeric nanoparticles as well as metal oxide coatings, to afford uniform hybrid fiber-like nanostructures. This work provides a versatile strategy toward the fabrication of narrow length dispersity continuous and segmented π-conjugated OPV-containing fiber-like micelles with the capacity to be decorated in a spatially selective way with varying functionalities.