Facile Processing of Unsubstituted π-Conjugated Aromatic Polymers through Water-solubilization Using Aromatic Micelles.

π-Conjugated aromatic polymers (πCAPs) are central components of functional materials yet suffer from insolubility without multiple covalent substituents on their backbones. We herein disclose a new strategy for the facile processing of unsubstituted heterocyclic πCAPs (i.e., poly(para-phenylene-2,6-benzobisoxazole) and poly(benzimidazobenzo-phenanthroline)), independent of the polymer length, via non-covalent encircling with aromatic micelles, composed of bent aromatic amphiphiles, in water. The UV/Visible studies reveal that the efficiencies of the present encircling method are ≈10 to 50-fold higher than those using conventional amphiphiles under the same conditions. The AFM and SEM analyses of the resultant aqueous polymer composites show that otherwise insoluble πCAPs form fine bundles (e.g., ≈1 nm in thickness) in the tubular aromatic micelles, through efficient π-stacking interactions. In the same way, pristine poly(para-phenylene) can be dissolved in water, displaying enhanced fluorescence (10-fold), relative to the polymer solid. Two types of unsubstituted πCAPs are likewise co-encircled in water, indicated by UV/Visible analysis. Importantly, aqueous processing of the encircled πCAPs into free-standing single- or multicomponent films with submicrometer thickness is demonstrated through a simple filtration-annealing protocol.
(© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)