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We report the formation of heavy alkali metal complexes of bicyclic host molecules including the caesium(I) complex that catches the central metal ion with the deep pocket of the host similar to a baseball glove. For this, three regioisomers of singly bridged calix[6]crown-6 [1,2-bridged (H 4 L 1,2 ), 1,3-bridged (H 4 L 1,3 ) and 1,4-bridged (H 4 L 1,4 )] have been synthesized by alkylation of calix[6]arene with pentaethylene glycol ditosylate in the presence of  M 2 CO 3  ( M  = Na, K, Rb and Cs). The larger the cation size of the metal carbonate, the higher the yield of the H 4 L 1,4  isomer, indicating the size-based template effect. A combination of H 4 L 1,2  and RbOH allowed isolation of the mononuclear rubidium(I) complex ( 1 ) in which the metal center is six-coordinated in a loose fashion, the remaining two oxygen donors in the crown loop and two phenols in the calix rim are uncoordinated. Notably, the complexation of H 4 L 1,2  with CsOH yielded the mononuclear caesium(I) complex ( 2 ), in which all possible ten binding sites on the deep and good-fit pocket participate in coordination via high cooperativity between the crown loop and calix rim, similar to a baseball glove. In dipolar organic solution, the caesium(I) complex  2  remains intact. H 4 L 1,4  afforded a dicesium(I) complex ( 3 ) and adjacent complexes are linked by intermolecular cation–π interactions, giving rise to a pseudo one-dimensional coordination polymer. These results provide insight into the metal carbonate-dependent synthesis of calix[6]crowns and the influence of regioisomers on caesium(I) complexation.

Regioisomers of singly bridged calix[6]crown-6 and their heavy alkali metal complexes: a molecular baseball glove for caesium(I)