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Novel Barium–Organic Incorporated Iodometalates: Do They Have Template Properties for Constructing Rare Heterotrimetallic Hybrids?

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posted on 03.11.2014, 00:00 authored by Shashank Mishra, Erwann Jeanneau, Gilles Ledoux, Stéphane Daniele
New barium–organic derivatives are introduced as countercations in the iodocuprates and -argentates to yield novel hybrids with unique structural motifs and bonding modes, many of them also showing vivid fluorescence on exposure to UV light. The tetrahedral MX4/trigonal-coplanar MX3 unit in these hybrids [Ba2(DMSO)12Cu8I12] (1) and [Ba­(tetraglyme)2]2[Ag8I12]·EtOH (7) can be replaced by the M′I4/M′I3 unit without compromising their basic structural motifs, thus leading to the formation of the rare mixed Cu–Ag iodometalates [Ba2(DMSO)12Cu4Ag4I12] (9) and [Ba­(tetraglyme)2]2[CuAg7I12]·EtOH (10), respectively. In contrast, a breakdown in the structure-directing properties of these iodometalates was observed in the mixed Ag–Pb iodometalate [Ba­(tetraglyme)2]2[Pb2Ag2I10]·2Me2CO (11), where the basic structure of the synthon [Ba­(tetraglyme)2]2[Ag4I8] (8) was not retained due to the compulsory molecular rearrangement required as a result of replacing AgI4/AgI3 units with octahedral PbI6 units.