Helical polymer scaffolds provide unique opportunities for the collective organization of functional elements such as ligands, dyes, electroactive and/or catalytically active elements. Applying recently developed strategies for self-assembly such as polymerization-induced self-assembly (PISA) and crystallization-driven self-assembly (CDSA) to these privileged templates yields unique asymmetric assemblies with potentials for the fabrication of next generation devices. In this regard, the primary thrust of our current investigations targets the development of bottom-up fabrication methods for the construction of precision inorganic nanostructures. Utilizing transition metal mediated living polymerizations of aryl isocyanides (AICs), we rapidly generate a diverse array of nanostructures with fine control of morphology, chirality and dimensions. Further, we present a robust modular strategy for attachment of a family of Ni(II) initiators to macromolecular coupling partners thereby enabling the synthesis of a variety of novel macroinitiator structures. Employing simple solvent tuning strategies, the targeted creation of a wide variety of nanostructures (i.e. 1D fibers, tapes, lamellae and superhelical bundles) is demonstrated. Performing PISA and CDSA in tandem, we generate seed particle dispersions suitable for PI-CDSA to rapidly afford highly ordered, uniform assemblies. Finally, using tandem AIC and ROMP polymerizations we attempt to synthesize bottle-brush unimolecular soft templates; we anticipate the approach will mitigate issues associated with the use of comparable micellar templates (i.e. mass transport/diffusional constraints).

Polyisocyanide self-assembly: From polymerization-induced self-assembly (PISA) to polymerization-induced crystallization-driven self-assembly (PI-CDSA)

ACS Spring 2022

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