New balls please! Reaction of Cu(BF4)2 with [(dach)PtII] (dach=trans (±)‐1,2‐diaminocyclohexane) and bis(ethylthio)methylenepropanedioate (BETMP) gave [{(dach)Pt(BETMP)}2Cu(BF4)2] (1; shown schematically). Dimerization of 1 in methanol leads to the first inorganic “tennis ball” 2 [Eq. (1)]. A BF4− ion is encapsulated in the cavity of 2.
An inorganic tennis ball with an empty cavity was formed without any assistance of guest molecules, and found to bind various anions selectively depending on their size and copper-anion interaction strengths without much change of the shapes.
Inorganic tennis balls (ITBs), [[{Pt(betmp)(dach)}(2)Cu](2)(X)][X](3) (in which X=ClO(4) (-) (3), NO(3) (-) (4), Cl(-) (5) and Br(-) (6); dach=trans-1,2-diaminocyclohexane and betmp=bisethylthiomethylidenepropanedioate) and [[{Pt(dteym)(dach)}(2)Cu](2)(PF(6))][PF(6)](3) (7; dteym=1,3-dithiepane-2-ylidenemalonate), were prepared as crystals. Investigation of their X-ray crystal structures revealed that shapes of the cavities in ITBs show significant distortions that depend on the properties of the encapsulated anions. The CuCu* distance was observed to be longest in 7 and shortest in 5, the difference between them being 2.05 A. The flexibility of cavity structures of ITBs makes it possible to encapsulate various anions inside the cavity, while their distortions may be a reason for the difference in the encapsulating ability for anions, that is, anion selectivity. Especially, the distortions observed in 7 are so severe that the encapsulating ability of the cavity for PF(6) (-) is very low compared to other anions. The shapes of ITBs with ClO(4) (-) and BF(4) (-) ions inside their cavities are very similar; however, ClO(4) (-) is encapsulated by the cavity better than BF(4) (-), which is explicable by the difference of metal-anion interactions. This structural study on ITBs gives a clue to the origin of the anion selectivity of the cavity in ITBs previously investigated by (19)F NMR spectroscopy of the ITBs in methanol.
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