Synthesis and Direct Observation of Chiral Supramolecular Polymer of Porphyrin Having Cholesteryl Groups

Langmuir. 2024 Mar 12;40(10):5535-5544. doi: 10.1021/acs.langmuir.4c00164. Epub 2024 Feb 26.

Abstract

We report the synthesis and microscopic investigations of two chiral helical porphyrin supramolecular polymers with different coordinating metals that are expected to be capable of serving as synthetic macromolecular motors driven by thermal fluctuations. Furthermore, based on their microscopic images, we propose a stepwise process for the formation of higher-order structures. These porphyrins formed completely different association states, and this was reflected in the marked differences in the shapes of the supramolecular polymers. The Cu-TChOAlaCPP supramolecular polymers formed H-aggregate rods in diisopropyl ether, then grew into superhelices and then into ribbons. On the other hand, Zn-TChOAlaCPP supramolecular polymers formed aggregates based on van der Waals interactions in diethyl ether, then grew into fibers and then grew into multiple-helices and ribbons. In addition, we imaged the interaction between long and short chains of the Cu-TChOAlaCPP supramolecular polymer by fast-scanning atomic force microscopy, and we indicated the availability as a macromolecular motor driven by thermal fluctuations.