Promoted Photocatalytic Hydrogen Evolution by Tuning the Electronic State of Copper Sites in Metal‐Organic Supramolecular Assemblies

Abstract The electronic state in terms of charge and spin of metal sites is fundamental to govern the catalytic activity of a photocatalyst. Herein, we show that modulation of the electronic states of Cu sites, without changing the coordination environments, of two metal‐organic supramolecular assemblies based on π⋅⋅⋅π stacking can significantly improve photocatalytic activity. The use of these heterogeneous photocatalysts, without using noble metal cocatalysts, resulted in an increase of the hydrogen production rate from 522 to 3620 μmol h −1 g −1 . A systematical analysis revealed that the charge density and spin density of the metal centers are efficiently modulated via the modulation of the coordination fields around active copper (II) centers by the variation of the non‐coordination groups of terminal ligands, leading to the significant enhancement of photocatalytic activity. This work provides an insight into the electronic state of active metal centers for designing high‐performance photocatalysts.