Supramolecular Anchoring of Fe(III) Molecular Redox Catalysts into Graphitic Surfaces Via CH-π and π-π Interactions for CO2 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. This generates a very well-defined catalysts-surface structure and electroactivity, together with a very large catalytic response. This approach represents a new anchoring strategy that can be applied to catalytic redox reactions in heterogeneous phase and compared to traditional methods involves about 4-5 orders of magnitude less mass deposition to achieve comparable activity and with very well-behaved electroactivity and stability.

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[3.1.0]hex-2-enes. The reaction scope was probed experimentally, and it was found that silyl-substituted benzenes provide the most rapid access to bicyclo[3.1.0]hexene derivatives, formed as single isomers with three stereogenic centers in yields up to 75% in one step. Two major mechanism hypotheses, both involving ESAA relief, were explored through quantum chemical calculations and experiments. The first mechanism involves protonation of excited-state benzene and subsequent rearrangement to bicyclo[3.1.0]hexenium cation, trapped by a nucleophile, while the second involves photorearrangement of benzene to benzvalene followed by protonation and nucleophilic addition. Our studies reveal that the second mechanism is operative. We also clarify that similar ESAA relief leads to puckering of S1-state silabenzene and pyridinium ion, where the photorearrangement of the latter is of established synthetic utility. Finally, we identified causes for the limitations of the reaction, information that should be valuable in explorations of similar photoreactions. Taken together, we reveal how the ESAA in benzene and 6π-electron heterocycles trigger photochemical distortions that provide access to complex three-dimensional molecular scaffolds from simple reactants.

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. Here, we design a porous CN photoanode connected to a highly active molecular Ru-based WOC, which also acts as an additional photo-absorber. We show that the strong interaction between the π-system of the heptazine units within the CN with the CH groups of the WOC's equatorial ligand enables a strong connection between them and an efficient electronic communication path. The optimized photoanode exhibits a photocurrent density of 180 ± 10 µA cm-2 at 1.23 V vs. the reversible hydrogen electrode (RHE) with 89% faradaic efficiency for oxygen evolution with turnover numbers (TONs) in the range of 3300 and a turnover frequency (TOF) of 0.4 s-1, low onset potential, extended incident photon to current conversion, and good stability up to 5 h. This study may lead to the integration of molecular catalysts and polymeric organic absorbers using supramolecular interactions.