Constructing π-Stacked Supramolecular Cage Based Hierarchical Self-Assemblies via π···π Stacking and Hydrogen Bonding

This is the authors' abstract. We don't add key points for this paper.

Constructing supramolecular cages with multiple subunits via weak intermolecular interactions is a long-standing challenge in chemistry. So far, π-stacked supramolecular cages still remain unexplored. Here, we report a series of π-stacked cage based hierarchical self-assemblies. The π-stacked cage (π-MX-cage) is assembled from 16 [MXL]⁺ ions (M = Mn²⁺, Co²⁺; X = Br⁻, SCN⁻, Cl⁻; and L = tris(2-benzimidazolylmethyl)amine) via 18 intermolecular π-stacking interactions. The tetrahedral cage, consisting of four [MXL]⁺ ions as the vertexes and six pairs of [MXL]⁺ ions as the edges, features 48 exterior N-H hydrogen bond donors for hydrogen bond formation with guest molecules. By variation of the M²⁺/X⁻ pair, the π-MX-cage demonstrates unique versatility for incorporating a wide variety of species via different hydrogen-bonding modes during the assembly of hierarchical superstructures. In specific, the π-MnBr-cages encapsulate acetonitrile (CH₃CN) or cis-1,3,5-cyclohexanetricarbonitrile (cis-HTN) molecules in the central voids, while a core-shell tetrahedral inorganic cluster [Mn(H₂O)₆]@([Mn(H₂O)₄]₄[Br₄²⁻]₆) (Mn@Mn₄-cage) is captured within the interstitial regions between cages. The π-CoSCN-cages are capable of stabilizing reactive sulfur-containing species, such as S₂O₄²⁻, S₂O₆²⁻, and HSO₃⁻ ions, in the hierarchical superstructure. Finally, H₂PO₄⁻ ions are incorporated between π-CoCl-cages, resulting in an inorganic mesoporous framework. These results provide insights into further exploring the chemistry and hierarchical assembly of supramolecular cages based on π-π stacking intermolecular interactions.