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

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.

研究人员将新型钡基有机衍生物（barium–organic derivatives）作为抗衡阳离子（countercations）引入碘铜酸盐（iodocuprates）与碘银酸盐体系，得到一系列具备独特结构基元（structural motifs）与成键模式（bonding modes）的新型杂化材料；其中多数材料在紫外光（UV light）照射下可展现出鲜明的荧光特性。在杂化物[Ba₂(二甲基亚砜（Dimethyl sulfoxide, DMSO）)₁₂Cu₈I₁₂]（1）与[Ba(四甘醇二甲醚（tetraglyme）)₂]₂[Ag₈I₁₂]·乙醇（EtOH）（7）中，四面体MX4与平面三角形MX3结构单元可被M′I4/M′I3单元替代且不会破坏其基本结构基元，据此分别得到了罕见的混合铜-银碘金属酸盐（mixed Cu–Ag iodometalates）[Ba₂(DMSO)₁₂Cu₄Ag₄I₁₂]（9）与[Ba(四甘醇二甲醚)₂]₂[CuAg₇I₁₂]·EtOH（10）。与之相反，在混合银-铅碘金属酸盐[Ba(四甘醇二甲醚)₂]₂[Pb₂Ag₂I₁₀]·2丙酮（Me₂CO）（11）中，这类碘金属酸盐的结构导向特性（structure-directing properties）遭到破坏：因将AgI4/AgI3单元替换为八面体PbI6结构单元而必须发生的分子重排，导致合成子（synthon）[Ba(四甘醇二甲醚)₂]₂[Ag₄I₈]（8）的基本结构无法得到保留。