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Updated: Nov 7, 2025

Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates
Published on: February 15, 2016
The [Ag25Cu4H8Br6(CCPh)12(PPh3)12]3+ : Ag13H8 silver hydride core protected by [CuAg3(CCPh)3(PPh3)3]+ motifs
Kaiyu Mikami1, Shen Hui1, Kazuyuki Kubo1
1Department of Chemistry, Graduate School of Science, Hiroshima University, Kagamiyama 1-3-1, Higashi-hiroshima 739-8526, Japan. tmizuta@hiroshima-u.ac.jp.
Abstract:
Copper alkynyl complexes [CuAg3(C[triple bond, length as m-dash]CAr)3(PPh3)3]+ (Ar = Ph, p-C6H4Me), in which three Ag(PPh3) units are bound among three C[triple bond, length as m-dash]CAr arms of trigonal-planar [Cu(C[triple bond, length as m-dash]CAr)3]2-, were selected as a protecting unit to cover the metal core of an atomically precise core-shell-type cluster. First, the formation of the protecting unit through the reaction of Cu(NCMe)4(PF6) with Ag(C[triple bond, length as m-dash]CAr) and PPh3 in a 1 : 3 : 3 ratio was confirmed. The reaction gave dimeric [CuAg3(C[triple bond, length as m-dash]CAr)3(PPh3)3]22+, in which the two planar [CuAg3(C[triple bond, length as m-dash]CAr)3(PPh3)3]+ units were stacked. Next, core-shell-type clusters were synthesized by adding NaBH4 and Et4NX (X = Cl, Br) to a solution similar to that used to prepare the protecting unit. The trigonal-planar protecting units nicely formed core-shell-type Ag nanoclusters formulated as [Ag13H8X6{CuAg3(C[triple bond, length as m-dash]CAr)3(PPh3)3}4]3+ (X = Cl, Ar = p-C6H4Me; X = Br, Ar = p-C6H4Me; X = Br, Ar = Ph). Their crystal structures revealed that the four [CuAg3(C[triple bond, length as m-dash]CAr)3(PPh3)3]+ units are linked by six halogen ions to form a tetrahedral cage that accommodates a polyhydride-Ag cluster formulated as Ag13H85+. As a concrete proof of the existence of the polyhydride, deuterated analogs Ag13D85+ were synthesized and subsequently characterized by high-resolution electrospray-ionization mass spectrometry measurements.
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