Aggregation-Induced Structural Symmetry Breaking Promotes Charge Separation for Efficient Photocatalytic Hydrogen...

Recently, organic semiconductors have received much attention in the field of photocatalysis due to their tunable physicochemical properties. However, organic semiconductor photocatalysts typically suffer from severe charge recombination due to high exciton binding energy. Herein, we found that aggregation of pyrene results in a red-shift of the light absorption from UV to visible light region. Importantly, the aggregation can induce dipole polarization by spontaneous structural symmetry breaking, thus significantly accelerating the separation and transfer of charge carriers. As a result, the pyrene aggregates display enhanced hydrogen photosynthesis activity. Furthermore, the noncovalent interactions allow rational design of physicochemical and electronic properties of pyrene aggregates, further strengthening the charge separation and photocatalytic activity of aggregates. The quantum yield of pyrene aggregates for hydrogen production highly reaches 20.77 % at 400 nm. Moreover, we have also observed pyrene analogues (1-hydroxypyrene, 1-nitropyrene and perylene) after aggregation all display large dipole moments induced by structural symmetry breaking and therefore accelerate the separation of charge carriers, confirming its general principle. This work highlights the achievement of using aggregation-induced structural symmetry breaking to enable the separation and transfer of charge carriers.