Supramolecular Engineering of Efficient Artificial Light-Harvesting Systems from Cyanovinylene Chromophores and Pillar[5]arene-Based Polymer Hosts.

Enhanced emission and adjustable wavelength for single luminogen systems are highly desirable in the scope of photoluminescent materials. Herein, a supramolecular strategy has been proposed for supramolecular assembly-induced enhanced emission and valid emission manipulation by fabricating an amphiphilic copolymer host material with pillar[5]arene units as the side chains, whereby cyanovinylene-based (CV) derivatives are anchored to the polymer hosts via host-guest interactions. The guest-bearing copolymers can further form luminescent supramolecular polymer nanoparticles (SPNs). Remarkably, the as-prepared SPNs exhibit dramatic emission enhancement and tunable fluorescence wavelength, ascribing to the synergetic effects involving the restriction of intramolecular motions and the prevented excimer formation for CV moieties, as endowed by host-guest interactions and the entanglement of the polymer chains. Furthermore, the SPNs can be established as efficient artificial light-harvesting systems via the inclusion of Nile red into the particles for broadened emission spectra. As a proof-of-concept study, the use of pillar[5]arene-containing polymer hosts largely facilitates the emission enhancement and wavelength adjustment for the inherent luminogens, setting the basis for the supramolecular design of highly tunable luminescent systems.