Supramolecular bottlebrush copolymers from crown-ether functionalized poly(p-phenylenevinylene)s†

The discovery of living, chain-growth polymerizations of poly(p-phenylenevinylene)s (PPVs) allows for low dispersed, controlled, and architecturally complex PPV-based polymers. This contribution presents the synthesis of PPVs functionalized with crown-ethers on each repeat unit that assemble with chain-end functionalized monotelechelic poly(styrene)s (PS) containing a terminal amine salt to form pseudorotaxane-based bottlebrush copolymers. The PPVs are synthesized by living ring-opening metathesis polymerization (ROMP) and the PS through atom-transfer radical polymerization (ATRP). The bottlebrush copolymer formation was confirmed by nuclear magnetic resonance spectroscopy, gel-permeation chromatography, isothermal titration calorimetry, dynamic light-scattering, wide-angle X-ray scattering, and optical spectroscopy. This work depicts the first example of a backbone modified PPV synthesized through ROMP and introduces a versatile strategy towards supramolecular bottlebrush copolymers containing conducting polymers. Our methodology lends itself to supramolecular materials for applications in chemical sensing, optoelectronics, and fluorescent imaging.