On the Interaction between Superatom Al(12)Be and DNA Nucleobases/Base Pairs: Bonding Nature and Potential Applications in O(2) Activation and CO Oxidation

[Image: see text] The interaction between quasi-chalcogen superatom Al(12)Be and DNA nucleobases/base pairs has been explored by searching for the most stable Al(12)Be–X (X = DNA bases and base pairs) complexes. Our results reveal that Al(12)Be prefers to combine with guanine by two Al–O and Al–N bonds rather than the other DNA bases, no matter in free state or base pair. The formed Al–N and Al–O bonds between Al(12)Be and DNA bases proved to be strong polar covalent bonds by the Wiberg bond index, nature bond orbitals, atoms in molecules theory, localized molecular orbitals, and electron localization functions analyses. More importantly, it is found that the formed global minimum of Al(12)Be–G has the ability to activate an oxygen molecule into a peroxide dianion (1)O(2)(2–), which can further catalyze the CO oxidation via the Eley–Rideal mechanism with a small energy barrier of 7.78 kcal/mol. We hope that this study could not only provide an in-depth understanding on the intermolecular interaction between metallic superatoms and DNA at the molecular level but also attract more interest in designing and synthesizing superatom-based heterogeneous catalysts with DNA/nucleobases as basic building blocks.