Functionalization of a [2]Catenane with Donor-Acceptor Chromophores Using a Metal Template and Click Reactions.

ABSTRACT

Synthesizing molecules with significant topological features, such as catenanes, tailored with specific groups to confer desired functionality, is essential for investigating various properties arising from the entanglement due to mechanical bonds. This investigation can pave the way for uncovering novel functional materials employing mechanically interlocked molecules (MIMs). In this direction, we have synthesized a p-donor (D) and p-acceptor (A) functionalized [2]catenane using a non-labile Co(III) metal ion as a template with pyridine-diamide templating center and utilizing click reaction for ring-closing. The donor group is a fluorene derivative, and the acceptor is a benzophenazine derivative, commonly employed in synthesizing conjugated polymers for various optoelectronic devices. Synthetically, the acceptor group was introduced into a macrocycle with a pyridine diamide unit. It was then threaded with a ligand having alkyne terminals to obtain the desired [2]pseudorotaxane utilizing cobalt ion as a template. Ring-closing was then performed with a di-azide functionalized molecule with the donor chromophore. The desired D-A functionalized [2]catenane is obtained after demetalation. All the starting materials, macrocycle, and entangled structures have been characterized by 1H-NMR, 13C-NMR, and mass spectroscopy. Some of these materials are also characterized by single-crystal X-ray analysis. The photophysical properties are studied by UV-visible and fluorescence spectroscopy.