A spectroscopic and structural study on the solvent-promoted stereospecific self-assembly of new Porphyrin-Bile Salt conjugates

The chiral bile salt sodium cholate has been covalently linked to tetra-aryl-porphyrins, conferring them an extrinsic chirality and obtaining new molecules with high tendency to aggregate in solution. The chirality transfer from the molecular to the nano- and meso-scale has been investigated by promoting the self-assembly of the conjugates balancing the ratio of aqueous/organic solvent mixtures and allowing a fine control of the dimensions and morphology of the final supramolecular architectures. The shift from elongated structures with helical ribbon features to monodisperse tubules or from tightly packed rolled sheets to wrapped scrolls was enabled by changing the solvent composition, with the possibility of forming tubular structures with a hollow cavity. From UV–Vis and Circular Dichroism (CD) spectroscopy the ability to self-assemble into J-type aggregates with a strong induction of supramolecular chirality was revealed, shedding light on a two-step process, with a fast monomer nucleation followed by a slow second step of further stereospecific chiral evolution. The results as a whole promote the new porphyrin-cholate conjugates as promising smart and easily tunable chiral materials for the design of stereoselective sensing devices.