Supramolecular BODIPY Dye Architectures for Advanced Light Harvesting and Energy Transfer Applications

Shape-persistent phenylacetylene macrocycles have been explored in a number of optoelectronic and light-harvesting applications, including two-photon absorption. Likewise, BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacenes) dyes have also been extensively used in material applications, owing to their tunable, intense absorption and sharp emission spectra exhibiting high quantum yields. Combining these two architectures, this thesis presents a derivative where a BODIPY is contained orthogonally within the phenylacetylene-macrocycle. This structure was inspired by photosystem II antennae complexes where energy is obsorbed by antennae complexes and funneled down to a reaction centre. Specifically, this family of molecules uses the phenylacetylene macrocycle to harvest the light and transfer it to the BODIPY core, and this has been observed by examining the fluorescence emission from the BODIPY (Figure 1). This novel dye design if coupled to a donor (D) and acceptor (A) capable of anchoring to TiO2 could be modified to become a π-spacer (i.e. D-π-A motif) for dye-sensitized solar cells resulting in panchromatic absorption, and ultimately more efficient devices.