Solvent-Assisted Supramolecular Assembly of Cyclotetrasiloxane–Functionalized Alkynylplatinum(II) Terpyridine Complexes

Abstract

Our present study demonstrated and explored the solvent effects on the association mechanism of the supramolecular nanomaterials in a series of cyclotetrasiloxane-appended alkynylplatinum(II) terpyridine complexes. Through the delicate balance of molecular interactions, some of these complexes were found to exhibit molecular association properties, with possible morphological transformation in response to solvent polarities. Twisted fibrils and nanoplates were apparent in aqueous and nonpolar media, respectively. Following the investigation of their molecular packing via powder X-ray diffraction and selected area electron diffraction experiments, we proposed a packing conformation, as follows: These nanostructure fabrications demonstrated to have been assisted by the presence of Pt···Pt interactions, in which the associated dramatic and rich spectroscopic response proceeded through mechanistic tracking of the assembly process. Further, nucleation and elongation modeling studies illustrated a solvent dependence of the association mechanism, with cooperative and isodesmic growth mechanism revealed in aqueous and apolar conditions, respectively.