Recent progresses in molecular-based artificial photosynthesis

Folding‐Induced Promotion of Proton‐Coupled Electron Transfers via Proximal Base for Light‐Driven Water Oxidation

“…Based on the combined analytical and kinetic data, we propose the following mechanistic picture for the excellent water oxidation catalysis with 2 C – 4 C . As shown previously, a hydrogen‐bonded H 2 O network can either be stabilized by cooperative effects within the cavities of macrocyclic Ru(bda) assemblies of different size by utilizing the carboxy groups of the bda ligands as directional bonding sites or via hydrogen‐bonding interactions to a protonated bipy site located opposite to the active site within a synthetic molecular cleft [22, 23, 42, 46] . In this work, we demonstrate the powerful effect of an auxiliary base in the ligand sphere on the catalytic performance of more flexible macrocycles of varying size.…”

“…As shown previously, a hydrogen‐bonded H 2 O network can either be stabilized by cooperative effects within the cavities of macrocyclic Ru(bda) assemblies of different size by utilizing the carboxy groups of the bda ligands as directional bonding sites or via hydrogen‐bonding interactions to a protonated bipy site located opposite to the active site within a synthetic molecular cleft. [ 22 , 23 , 42 , 46 ] In this work, we demonstrate the powerful effect of an auxiliary base in the ligand sphere on the catalytic performance of more flexible macrocycles of varying size. Single‐crystal X‐ray analysis of the multinuclear series 2 C – 4 C showed that within the larger complexes 3 C and 4 C , intramolecular π‐π interactions of the trans ‐oriented bipy units put the proximal base in close proximity to the active sites.…”

Mechanistic Insights into Photochemical CO2 Reduction to CH4 by a Molecular Iron–Porphyrin Catalyst

“…Artificial photosynthesis, inspired by nature and powered by solar energy, offers a viable solution to synthesize value-added chemicals by using CO 2 as a carbon-based synthon, accomplishing a sustainable carbon cycle and alleviating reliance on fossil fuels. − Owing to the thermodynamic stability and kinetic inertness of CO 2 , the required potential for single-electron reduction of the linear CO 2 molecule to the bent CO 2 •– radical anion is highly negative (at −1.90 V vs NHE in N , N -dimethylformamide solution), thus impeding the subsequent multi-electron/proton reduction to produce hydrocarbons. Meanwhile, the low-valent electron-rich metal center can not only react with CO 2 but also undertake the hydrogen evolution reaction (HER) pathway to reduce protons in the solution. , Hence appropriate methods are required to promote the CO 2 reduction reaction (CO 2 RR) while suppressing the HER for selective CO 2 reduction.…”

Folding‐Induced Promotion of Proton‐Coupled Electron Transfers via Proximal Base for Light‐Driven Water Oxidation

“…[45] Based on the combined analytical and kinetic data, we propose the following mechanistic picture for the excellent water oxidation catalysis with 2 C-4 C. As shown previously, a hydrogen-bonded H 2 O network can either be stabilized by cooperative effects within the cavities of macrocyclic Ru-(bda) assemblies of different size by utilizing the carboxy groups of the bda ligands as directional bonding sites or via hydrogen-bonding interactions to a protonated bipy site located opposite to the active site within a synthetic molecular cleft. [22,23,42,46] In this work, we demonstrate the powerful effect of an auxiliary base in the ligand sphere on the catalytic performance of more flexible macrocycles of varying size. Single-crystal X-ray analysis of the multinuclear series 2 C-4 C showed that within the larger complexes 3 C and 4 C, intramolecular π-π interactions of the trans-oriented bipy units put the proximal base in close proximity to the active sites.…”