Homo- and Heteromultinuclear Pseudocapsules Assembled from Calix[6]-mono-crown-5 and Alkali Metal Ions

The formation of pseudocapsule type homo- and heteromultinuclear complexes of calix[6]-mono-crown-5 (H₄L) encapsulating from 4 to 6 alkali metal ions is reported. H₄L reacts with KOH to yield a hexanuclear potassium(I) complex [K₆(HL)₂(CH₃OH)₂]·CHCl₃ (1) in which two bowl-shaped tripotassium(I) complex units are linked in a rim-to-rim fashion via the interligand C-H···π interactions. In the same reaction condition, RbOH afforded a tetranuclear rubidium(I) complex [Rb₄(H₂L)₂(CH₃OH)₂(μ-H₂O)₂]·6CHCl₃ (2). In 2, again two bowl-shaped dirubidium(I) complex units are held together by two bridging water molecules and C-H···π interactions that act as a glue to generate such an elegant pseudocapsule. Interestingly, a mixture of KOH and RbOH yielded a heterotetranuclear complex [K₂Rb₂(H₂L)₂(CH₃OH)₂(μ-H₂O)₂]·6CHCl₃ (3). Similarly, two heterodinuclear bowl units [KRb(H₂L)] in 3 are held together by two bridging water molecules and C-H···π interactions to form a heteromultinuclear pseudocapsule. In each heterodinuclear K⁺/Rb⁺ bowl unit of 3, Rb⁺ occupies the center of the crown loop while K⁺ locates inside the calix rim. Consequently, the proposed host discriminates not only on the types and numbers of the metal ions but also on their positional preferences in forming pseudocapsules. Solution studies by nuclear magnetic resonance and electrospray ionization-mass support the heterometallic (K⁺/Rb⁺) complexation by showing the superior binding affinity of Rb⁺ over K⁺ toward the crown loop. These results demonstrate how the metal-driven pseudocapsules are formed and present a new perspective on the metallosupramolecules of the calixcrown scaffold.