Supramolecular interaction of a molecular catalyst with a polymeric carbon nitride photoanode enhances photoelectrochemical activity and stability at neutral pH.

Polymeric carbon nitride (CN) emerged as an alternative, metal-free photoanode material for water-splitting photoelectrochemical cells (PECs). However, the performance of CN photoanodes is limited due to the slow charge separation and water oxidation kinetics due to poor interaction with water oxidation catalysts (WOCs). Moreover, operation under benign, neutral pH conditions is rarely reported.

Supramolecular Anchoring of Fe(III) Molecular Redox Catalysts into Graphitic Surfaces Via CH-π and π-π Interactions for CO Electroreduction.

Photoelectrochemical devices require solid anodes and cathodes for the easy assembling of the whole cell and thus redox catalysts need to be deposited on the electrodes. Typical catalyst deposition involves drop casting, spin coating, doctor blading or related techniques to generate modified electrodes where the active catalyst in contact with the electrolyte is only a very small fraction of the deposited mass. We have developed a methodology where the redox catalyst is deposited at the electrode based on supramolecular interactions, namely CH-π and π-π between the catalyst and the surface.

Impact of Excited-State Antiaromaticity Relief in a Fundamental Benzene Photoreaction Leading to Substituted Bicyclo[3.1.0]hexenes.

Benzene exhibits a rich photochemistry which can provide access to complex molecular scaffolds that are difficult to access with reactions in the electronic ground state. While benzene is aromatic in its ground state, it is antiaromatic in its lowest ππ* excited states. Herein, we clarify to what extent relief of excited-state antiaromaticity (ESAA) triggers a fundamental benzene photoreaction: the photoinitiated nucleophilic addition of solvent to benzene in acidic media leading to substituted bicyclo[3.