Amphiphilicity-Controlled Polychromatic Emissive Supramolecular Self-Assemblies for Highly Sensitive and Efficient Artificial Light-Harvesting Systems.

Dynamic sequential control of photoluminescence by supramolecular approaches has become a great issue in supramolecular chemistry. However, developing a systematic strategy to construct polychromatic photoluminescent supramolecular self-assemblies for improving the efficiency and sensitivity of artificial light-harvesting systems still remains a challenge. Here, a series of amphiphilicity-controlled supramolecular self-assemblies with polychromatic fluorescence based on lower-rim hexyl-modified sulfonatocalix[4]arene (SC4A6) and N-alkyl-modified p-phenylene divinylpyridiniums (PVPn, n = 2-7) as efficient light-harvesting platforms is reported. PVPn shows wide ranges of polychromatic fluorescence by co-assembling with SC4A6, whose emission trends significantly depend on the modified alkyl-chains of PVPn. The formed PVPn-SC4A6 co-assemblies as light-harvesting platforms are extremely sensitive for transferring the energy to two near-infrared emissive acceptors, Nile blue (NiB) and Rhodamine 800. After optimizing the amphiphilicity of PVPn-SC4A6 systems, the PVPn-SC4A6-NiB light-harvesting systems achieve an ultrasensitive working concentration for NiB (2 nm) and an ultrahigh antenna effect up to 91.0. Furthermore, the two different kinds of light-harvesting nanoparticles exhibit good performance on near-infrared imaging in the Golgi apparatus and mitochondria, respectively.