Probing the influence of substrate binding on photocatalytic dehalogenation with a heteroleptic supramolecular [M4La2Lb2] square containing PDI photosensitizers as ligands

Photoredox catalysis is a valuable tool in a large variety of chemical reactions. Main challenges still to be overcome are photodegradation of photocatalysts and substrates, short lifetimes of reactive intermediates, and selectivity issues due to unwanted side reactions. A potential solution to these challenges is the pre-organization of the photosensitizer, substrate and (co)-catalyst in supramolecular self-assembled structures. In such architectures, (organic) dyes can be stabilized, and higher selectivity could potentially be achieved through pre-organizing desired reaction partners via non-covalent interactions. Perylene diimide (PDI) is an organic dye, which can be readily reduced to its mono- and dianion. Excitation of both anions leads to highly reducing excited states, which are able to reduce a variety of substrates via single electron transfer. The incorporation of PDI into a heteroleptic [(M4L2L2b)-L-a] supramolecular square has been recently demonstrated. Herein we investigate its photophysical properties and demonstrate that incorporated PDI indeed features photocatalytic activity. Initial results suggest that the pre-organisation by binding positively affects the outcome.

Automated summary

Photoredox catalysis is a valuable tool in various chemical reactions, but it faces challenges such as photodegradation of photocatalysts and substrates, short lifetimes of reactive intermediates, and selectivity issues due to unwanted side reactions. One potential solution is the pre-organization of photosensitizers, substrates, and (co)-catalysts in supramolecular self-assembled structures, which can stabilize dyes and improve selectivity through non-covalent interactions.