Selective CO2 adsorption and bathochromic shift in a phosphocholine-based lipid and conjugated polymer assembly.

We assemble a film of a phosphocholine-based lipid and a crystalline conjugated polymer using hydrophobic interactions between the alkyl tails of the lipid and alkyl side chains of the polymer, and demonstrated its selective gas adsorption properties and the polymer's improved light absorption properties. We show that a strong attractive interaction between the polar lipid heads and CO2 was responsible for 6 times more CO2 being adsorbed onto the assembly than N2, and that with repeated CO2 adsorption and vacuuming procedures, the assembly structures of the lipid-polymer assembly were irreversibly changed, as demonstrated by in situ grazing-incidence X-ray diffraction during the gas adsorption and desorption. Despite the disruption of the lipid structure caused by adsorbed polar gas molecules on polar head groups, gas adsorption could promote orderly alkyl chain packing by inducing compressive strain, resulting in enhanced electron delocalization of conjugated backbones and bathochromic light absorption. The findings suggest that merging the structures of the crystalline functional polymer and lipid bilayer is a viable option for solar energy-converting systems that use conjugated polymers as a light harvester and the polar heads as CO2-capturing sites.

Strong Bathochromic Shift of Conjugated Polymer Nanowires Assembled with a Liquid Crystalline Alkyl Benzoic Acid via a Film Dispersion Process.

We present aqueous dispersions of conjugated polymer nanowires (CPNWs) with improved light absorption properties aimed at aqueous-based applications. We assembled films of a donor-acceptor-type conjugated polymer and liquid crystalline 4-n-octylbenzoic acid by removing a cosolvent of their mixture solutions, followed by annealing of the films, and then formed aqueous-dispersed CPNWs with an aspect ratio >1000 by dispersing the films under ultrasonication at a basic pH. X-ray and spectroscopy studies showed that the polymer and liquid crystal molecules form independent domains in film assemblies and highly organized layer structures in CPNWs. Our ordered molecular assemblies in films and aqueous dispersions of CPNWs open up a new route to fabricate nanowires of low-band-gap linear conjugated polymers with the absorption maximum at 794 nm remarkably red-shifted from 666 nm of CPNWs prepared by an emulsion process. Our results suggest the presence of semicrystalline polymorphs ß1 and ß2 phases in CPNWs due to long-range π-π stacking of conjugated backbones in compactly organized lamellar structures. The resulting delocalization with a reduced energy bang gap should be beneficial for enhancing charge transfer and energy-conversion efficiencies in aqueous-based applications such as photocatalysis.