Synergetic Self-Assembly of Liquid Crystalline Block Copolymer with Amphiphiles for Fabrication of Hierarchical Assemblies.

Novel functions and advanced structure, where each single component could not be produced individually, can exhibit from the collective and synergistic behavior of component systems. This synergetic strategy has been successfully demonstrated for co-assembly of polymer-polymer to construct hierarchical nanomaterials. However, differences in the natures of polymer and small molecules impose challenges in the construction of sophisticated co-assemblies with geometrical and compositional control. Herein, a synergetic self-assembly strategy is proposed to prepare organic-organic hybrid colloidal mesostructures by blending a liquid crystalline block copolymer (LC-BCP) with small molecular amphiphiles. Through a classic solvent-exchange process, amphiphiles embedded with LC-BCP realize multi-component nucleation and hierarchical assembly driven by anisotropic interaction from the LC ordering alignment of the core-forming block. 1D nanofibers with a periodic striped structure are formed by further LC component fusion and refinement. In addition, LC ordering effect of LC-BCP can be regulated by selecting appropriate solvents and leads to the formation of vesicular co-micelles. By means of the thermal-responsive behavior of amphiphiles, hexagonal pore arrays are finally generated on the surface of those vesicles.

Asymmetric Living Supramolecular Polymerization: Precise Fabrication of One-Handed Helical Supramolecular Polymers.

Programming the organization of semiconducting polymers to form well-defined nanoarchitectures is desirable for fabricating functional materials. In this work, semiconducting copolymers, poly(cholesterol allene)-b-poly(3-hexylthiophene) (PCA-b-P3HT) containing helical PCA and poly(alkoxy allene)-b-poly(3-hexylthiophene) (PAA-b-P3HT) containing achiral PAA segments, were prepared. Crystallization of P3HT and helicity of PCA drove PCA-b-P3HT self-assemble into spherical nanoparticles that gradually transformed into one-handed helical nanofibers. The chirality of PCA was transferred to the supramolecular architectures, induced high optical activity in P3HT. Interestingly, the chiral seed micelles of PCA-b-P3HT induced asymmetric copolymerization of achiral PAA-b-P3HT, which led to helical supramolecular block copolymers with defined helicity and controlled length. Remarkably, the supramolecular copolymers showed white-light emission and circularly polarized luminescence.