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. A series of amphiphilicity‐controlled polychromatic emissive supramolecular self‐assemblies is constructed as highly sensitive and efficient artificial light‐harvesting platforms. Two near‐infrared emissive light‐harvesting acceptors are employed to achieve the highest antenna effect up to 91.0 and most sensitive working concentration (2 nm). Such near‐infrared emissive light‐harvesting systems show good capability for imaging in both the Golgi apparatus and mitochondria.