A 116-Nuclear Metallosupramolecular Cage-of-Cage Showing Multistep Single-Crystal-to-Single-Crystal Transformation

Abstract

Here a unique single-crystal-to-single-crystal (SCSC) transformation of a 116-nuclear Au^I ₇₂ Cd^II ₄₀ Na^I ₄ cage-of-cage (2_CdNa ) is reported, which was created from a trigold(I) metalloligand with d-penicillamine by way of a 9-nuclear Au^I ₆ Cd^II ₃ cage (1). Cage-of-cage 2_CdNa is composed of 12 cages of 1 that are linked by 4 Cd²⁺ and 4 Na⁺ ions, with its surface being covered by 12 NO₃ ^- ions to form a discrete, spherical molecule with a diameter ca. 4.7 nm. In crystal 2_CdNa , the cage-of-cage molecules are packed in a cubic lattice with a huge cell volume of ca. 4.5×10⁵ ų _, so as to have large interstices with diameters of more than 3 nm. Upon soaking crystals 2_CdNa in aqueous Cu(NO₃ )₂ , all Cd²⁺ and Na⁺ were quickly exchanged by Cu²⁺ to produce an analogous Au^I ₇₂ Cu^II ₄₄ cage-of-cage (2_Cu ) in a SCSC manner. Prolonged soaking led to the SCSC transformation to another supramolecular structure (2'_Cu ) consisting of 152-nuclear Au^I ₇₂ Cu^II ₈₀ cage-of-cages that are alternately H-bonded with the Au^I ₇₂ Cu^II ₄₄ cage-of-cages. 2'_Cu showed the accommodation of MoO₄ ^2- and the conversion of MoO₄ ^2- to β-Mo₈ O₂₆ ^4- in the crystal, with retention of single-crystallinity.

Keywords: cage compounds; heterometallic complexes; nanostructures; polyoxometalates; solid-state reactions.