Covalent post-assembly modification of π-conjugated supramolecular polymers delivers structurally robust...

A two-component stapling strategy is used to covalently tether a new class of water-soluble supramolecular polymers built from bay-functionalized perylene bisimide (PBI) units. By leveraging a novel combined strategy where excitonic coupling and fluorescence data are exploited as spectroscopic reporters, structural design principles are established to form light-harvesting superstructures whose ground-state electronic properties are not sensitive to solvation environments. Moreover, we interrogate the structural properties of stapled superstructures by capitalizing on the drastic changes in fluorescence quantum yields against parent supramolecular assemblies. In essence, our work shows that the combination of excitonic coupling measurements and photoluminescence experiments delineates a more accurate understanding of the design principles required to limit the degree of structural defects and magnify short- and long-range electronic couplings between redox-active units in this new class of solvated nanoscale objects. These results highlight that the fragile conformation of non-covalent assemblies, which are regulated by weak secondary interactions, can be preserved by post-assembly modification of preformed supramolecular polymers. These synthetic and spectroscopic principles can in turn be codified as experimental handles to parameterize the optoelectronic properties of light-harvesting nanoscale objects.