Aryl Boronic Acids in Columnar Stacked Co-crystalline Materials: Key-Factors Governing the Assembly with Quinones

The assembly of aryl boronic acids B with quinones Q into columnar mixed stacked materials, as previously observed in the solid-state, has been here subjected to a detailed theoretical analysis focusing on the properties of the isolated synthons (HOMO-LUMO energies, electron affinity, ionization potential, reorganization hole/electron energies, partial Hirshfeld atomic charges and conformation stabilities) as well as those of the 1 : 1 adducts (Hirshfeld analysis, IRI surfaces, Hirshfeld atomic charges, hydrogen bond and slipped stacked π-π contributions). The overall picture obtained throught this study shows an intricate pattern of interconnected factors contributing to the formation and stability of the B_xQ_y adducts, and it unveils the importance of parameters such as HOMO-LUMO gap, polarization and charge transfer, in addition to the more evident hydrogen bond and slipped-stacked π-π interactions in the formation of 1 : 1 adducts. An explanation has been also given for the presence in some B_xQ_y adducts of the rare anti-anti conformation for the BO−H group with respect to the most studied and common anti-syn conformation.