Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
BCSJ Award Article
Extraordinary Aggregation of Inorganic Anions in Chiral Metallosupramolecular Ionic Crystals
Raeeun LeeAsako Igashira-KamiyamaMitsutaka OkumuraTakumi Konno
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2013 Volume 86 Issue 8 Pages 908-920


An optically active AuI4CoIII2 complex with mixed D-penicillaminate (D-pen) and 1,2-bis(diphenylphosphino)ethane (dppe), [Au4Co2(dppe)2(D-pen)4]2+, was selectively formed from [Au2(dppe)(D-pen)2]2− and CoIII. When this complex was crystallized with monovalent anions (ClO4, BF4, NO3, Cl, Br, and N3), the AuI4CoIII2 complex cations were self-assembled to form +12-charged supramolecular octahedrons that are closely packed in a face-centered cubic (fcc) structure. In this structure, ten monovalent anions are accommodated in each hydrophilic tetrahedral interstice to create an adamantane-shaped anionic cluster, while two anions are each encapsulated in each octahedral interstice and in the center of each supramolecular octahedron. The use of divalent anions (SO42− and SiF62−) also produced an analogous fcc structure made up of the +12-charged supramolecular octahedrons. In this case, six divalent anions are accommodated in each hydrophilic tetrahedral interstice to form an octahedron-shaped anionic cluster, completing a giant zinc blende lattice structure where all cations and anions are separately aggregated into the +12-charged octahedrons and the −12-charged octahedrons, respectively. The site selective aggregation of two kinds of inorganic anions (PF6/Br, BF4/Br, and NO3/Br) in the fcc structure, along with the synthesis and characterization of an analogous AuI4CrIII2 complex, is also reported.

The cationic AuI4MIII2 (M = Co and Cr) hexanuclear complexes are crystallized with certain inorganic anions to form ionic crystals, in which inorganic anions are aggregated into amazing anionic clusters accompanied by the aggregation of the AuI4MIII2 cations into supramolecular octahedrons. Fullsize Image
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© 2013 The Chemical Society of Japan
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