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nido-Cage···π Bond: A Non-covalent Interaction between Boron Clusters and Aromatic Rings and Its Applications.

Exploration and comprehension of chemical bonding is one of the central tasks in chemistry. To date, non-covalent interactions involving multicenter multielectron skeletons like boron clusters is rarely reported. Here, a non-covalent interaction, nido-cage···π bond, is discovered based on the boron cluster C2B9H12- and an aromatic π system. The X-ray diffraction studies indicate that the nido-cage···π bonding presents parallel-displaced or T-shaped geometries. The contacting distance between cage and π ring varies with the type and the substituent of the aromatic ring. The theoretical calculations reveal that this nido-cage···π  bond shares a similar nature to the conventional anion···π or π···π bonds found in classical aromatic ring systems. Besides, such a  nido-cage···π interaction induces variable photophysical properties such as aggregation-induced emission and aggregation-caused quenching in one molecule. This work offers an overall understanding towards the boron cluster-based non-covalent bond and opens a door to investigate its properties.