Solvent induced helical aggregation in the self-assembly of cholesterol tailed platinum complexes

Abstract

Three alkynylplatinum(II) bipyridyl complexes in which two cholesterol groups are combined with a bipyridyl group via alkyl chains and amido bonds were designed and synthesized. The complexes have different lengths of ethylene glycol chains at the para-position of 1-phenylethyne. All three complexes can self-assemble to gel networks in DMSO, while only the morphology of 1a without an ether chain shows a well-defined right-handed helical structure in layer packing mode. However, 1c with long ethylene glycol chains forms perfect regular left-handed helical structures in aqueous ethanol solution while the volume percentage of water is less than 5% (v/v). As the ratio of water increases, the chirality changes from a left-handed helix to a right-handed helix and the packing mode alters from a monolayer structure to a hexagonal structure. As the ratio of water further increases to greater than 50% (v/v), the structure of the assembly finally transforms into bilayer vesicles. The process of the morphology transition is traced by circular dichroism spectra, powder X-ray diffraction, SEM and TEM images. The result indicates that a polar solvent (water) acts as a trigger to change the self-assembly of the chiral structures of the complex due to the strong hydrophobic interaction between cholesterol groups and the balance of the hydrophobicity and hydrophilicity of the solvent environment.