Energy funnelling within multichromophore architectures monitored with subnanometre resolution

Abstract

In natural and artificial light-harvesting complexes (LHC) the resonant energy transfer (RET) between chromophores enables an efficient and directional transport of solar energy between collection and reaction centers. The detailed mechanisms involved in this energy funneling are intensely debated, essentially because they rely on a succession of individual RET steps that can hardly be addressed separately. Here, we developed a scanning tunnelling microscopy-induced luminescence (STML) approach allowing visualizing, addressing and manipulating energy funneling within multi-chromophoric structures with sub-molecular precision. We first rationalize the efficiency of the RET process at the level of chromophore dimers. We then use highly resolved fluorescence microscopy (HRFM) maps to follow energy transfer paths along an artificial trimer of descending excitonic energies which reveals a cascaded RET from high- to low-energy gap molecules. Mimicking strategies developed by photosynthetic systems, this experiment demonstrates that intermediate gap molecules can be used as efficient ancillary units to convey energy between distant donor and acceptor chromophores. Eventually, we demonstrate that the RET between donors and acceptors is enhanced by the insertion of passive molecules acting as non-covalent RET bridges. This mechanism, that occurs in experiments performed in inhomogeneous media and which plays a decisive role in fastening RET in photosynthetic systems, is reported at the level of individual chromophores with atomic-scale resolution. As it relies on organic chromophores as elementary components, our approach constitutes a powerful model to address fundamental physical processes at play in natural LHC.