Interfacing Flexible Design and Social Self-Sorting Enables Comprehensive Control over Photophysical and Self-Assembly Properties of Supramolecular Polymers.

Supramolecular self-assembly offers an intriguing approach to construct microarchitectures, which combine properties of their molecular constituents with dynamic supramolecular features. Control over intermolecular interactions and their resulting properties can sometimes be achieved by targeted design. However, it is often unfeasible to transfer the insights gained from a specific supramolecular synthon to another chromophore without tedious synthetic work guided by trial and error. Herein we demonstrate how a flexible molecular design approach enables access to a diverse library of photophysical properties, which can be further diversified by social self-sorting strategies using a second supramolecular building block as a modulator. By intercalation into the supramolecular polymer the modulator can disrupt interchromophore interactions and modulate the ensembles emissive properties across the visible color space by simply adjusting the ratio between the two building blocks. Furthermore, by combining a chromophore appended synthon with a different morphology than the modulator the mesoscopic size distribution of the coassemblies can be modified to resemble either of its constituents. Crucially, this moldability is not only achievable for systems under thermodynamic control, but can be also employed to tune photophysical properties and thermal stability profiles of kinetically controlled states. Finally, the thermodynamic stability of the modulated polymers can be adjusted by varying the amount of solubilizing alkyl chains in the ensemble. This peripheral stabilization approach does not affect the engineered photophysical or supramolecular properties. Our results demonstrate how flexible molecular design enriched by a supramolecular modulator can offer access to a wide variety of photophysical properties and enable unique fine-tuning of various supramolecular properties.