CO₂ Photoactivation Study of Adenine Nucleobase: Role of Hydrogen‐Bonding Traction

Abstract The discovery and in‐depth study of non‐biocatalytic applications of active biomolecules are essential for the development of biomimicry. Here, the effect of intermolecular hydrogen‐bonding traction on the CO₂ photoactivation performance of adenine nucleobase by means of an adenine‐containing model system (AMOF‐1−4) is uncovered. Remarkably, the hydrogen‐bonding schemes around adenines are regularly altered with the increase in the alkyl (methyl, ethyl, isopropyl, and tert‐butyl) electron‐donating capacity of the coordinated aliphatic carboxylic acids, and thus, lead to a stepwise improvement in CO₂ photoreduction activity. Density functional theory calculations demonstrate that strong intermolecular hydrogen‐bonding traction surrounding adenine can obviously increase the adenine‐CO₂ interaction energy and, therefore, result in a smoother CO₂ activation process. Significantly, this work also provides new inspiration for expanding the application of adenine to more small‐molecule catalytic reactions.