Exploration and comprehension of chemical bonding is one of the central tasks in chemistry. Here, a new non‐covalent interaction, a nido‐cage···π bond, is discovered in a collaborative work between Deshuang Du and Prof. Yan from Nanjing University and Prof. Jordi Poater at the University of Barcelona (previous DiMoCat member) and Prof. Miquel Solà from the DiMoCat group of the Institute of Computational Chemistry and Catalysis of the University of Girona. The new interaction found is between the boron cluster C₂B₉H₁₂^‐ and several aromatic π systems. The X‐ray diffraction studies indicate that the nido‐cage···π bonding presents parallel‐displaced or T‐shaped geometries. The theoretical calculations confirms 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.

Tu, D.; Yan, H.; Poater, J.; Solà, M. “nido‐Cage···π Bond: A Non‐covalent Interaction between Boron Clusters and Aromatic Rings and Its Applications” Angew. Chem. Int. Ed. 2020,  DOI: 10.1002/anie.201915290