A Donor-Acceptor [2]Catenane for Visible Light Photocatalysis

Colored charge-transfer complexes can be formed by the association between electron-rich donor and electron-deficient acceptor molecules, bringing about the narrowing of HOMO-LUMO energy gaps so that they become capable of harnessing visible light. In an effort to facilitate the use of these widespread, but nonetheless weak, interactions for visible light photocatalysis, it is important to render the interactions strong and robust. Herein, we employ a well-known donor-acceptor [2]catenane-formed by the mechanical interlocking of cyclobis(paraquat-p-phenylene) and 1,5-dinaphtho[38]crown-10-in which the charge-transfer interactions between two 4,4'-bipyridinium and two 1,5-dioxynaphthalene units are enhanced by mechanical bonding, leading to increased absorption of visible light, even at low concentrations in solution. As a result, since this [2]catenane can generate persistent bipyridinium radical cations under continuous visible-light irradiation without the need for additional photosensitizers, it can display good catalytic activity in both photo-reductions and -oxidations, as demonstrated by hydrogen production.in the presence of platinum nanoparticles.and aerobic oxidation of organic sulfides, such as L-methionine, respectively. This research, which highlights the usefulness of nanoconfinement present in mechanically interlocked molecules for the reinforcement of weak interactions, can not only expand the potential of charge-transfer interactions in solar energy conversion and synthetic photocatalysis but also open up new possibilities for the development of active artificial molecular shuttles, switches, and machines.

Automated summary

This study enhances the charge-transfer interactions between donor and acceptor molecules through mechanical interlocking, leading to increased absorption of visible light and good catalytic activity. The [2]catenane demonstrated excellent performance in both photo-reductions and -oxidations, showing potential for solar energy conversion and development of active artificial molecular shuttles, switches, and machines.