Cascade Energy Transfer in Biopolymer-Templated Multi-Chromophoric Assemblies: Ratiometric Temperature Sensing

Natural light-harvesting complexes collect energy from sunlight and transfer it to the reaction center through a cascade of energy and electron transfer steps. Artificial light-harvesting systems functioning in aqueous media mimic natural photosynthetic systems. However, their design remains a challenging task as closely packed antenna chromophores often undergo severe self-quenching. Herein, we report luminescent co-assemblies between cationic pyrene-appended imidazolium amphiphiles and two anionic biopolymeric scaffolds, heparin and DNA in aqueous media. These co-assemblies served as excellent platforms for constructing artificial light-harvesting systems as upon co-embedding of multiple external dyes, highly efficient single-step and cascade energy transfer was observed from the pyrene donors to the acceptor dyes. Most notably, the efficiency of the energy transfer process was possible to modulate by employing multiple stimuli such as pH and temperature, and this resulted in the generation of multi-color luminescent materials in solution and film states, and they were also exploited in ratiometric temperature sensing. Their stimuli-responsive luminescence in the solid state was found to be advantageous for encryption studies.