An [MS₄Cu_x]^x−2 cluster unit (M = W, Mo, x = 1, 2,…6) is a kind of heterothiometallic unit of versatile connectivities and geometries for building metal–organic frameworks (MOFs) of intriguing structures and properties. We here report two MOFs based on the [WS₄Cu_x]^x−2 unit and a MOF based on the [MoS₄Cu_x]^x−2 unit with 9,10-di(pyridin-4-yl)anthracene (dpa). 1 contains penta-nuclear [WS₄Cu₄]²⁺ units, which act as tetrahedral nodes and are linked by dpa ligands into a 5-fold interpenetrated diamondoid network. 2 contains an unprecedented [WS₄Cu₆]⁴⁺·I⁻·[WS₄Cu₆]⁴⁺ unit where two hepta-nuclear [WS₄Cu₆]⁴⁺ units are bridged by an I⁻ ion, which acts as a 7-connector node, leading to a 3D network with the rare hxg-d topology. 3 is built from penta-nuclear [MoS₄Cu₄]²⁺ units and dpa ligands and is isostructural to 1. The structural difference between 1 and 2 should come from the isomerization of the [WS₄Cu_x]^x−2 unit in the synthesis processes, and we found that temperature was much more important than other factors, such as solvent, the halide anion of the Cu^I salt and the ratio of [NH₄]₂WS₄ to Cu^I salt, for the isomerization of the [WS₄Cu_x]^x−2 unit in the formation of 1 and 2.

中文翻译：

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由 [MS4Cux]x−2 (M = W, Mo) 单元构建的金属-有机框架：温度引起的簇单元异构化

[MS ₄ Cu _x ] ^{x -2}簇单元 (M = W, Mo, x = 1, 2,…6) 是一种具有多功能连接性和几何形状的异硫金属单元，用于构建金属有机框架 (MOF)结构和特性。我们在此报告了两种基于 [WS ₄ Cu _x ] ^{x -2}单元的 MOF 和基于 [MoS ₄ Cu _x ] ^{x -2}单元与 9,10-di(pyridin-4-yl) anthracene (dpa ）。1包含五核 [WS ₄ Cu ₄ ] ²⁺单元，它们充当四面体节点，并通过 dpa 配体连接成 5 重互穿菱形网络。2包含一个前所未有的 [WS ₄ Cu ₆ ] ⁴⁺ ·I ^- ·[WS ₄ Cu ₆ ] ⁴⁺单元，其中两个七核 [WS ₄ Cu ₆ ] ⁴⁺单元由一个 I ^-离子桥接，作为一个 7 连接器节点，导致具有罕见的hxg-d拓扑的 3D 网络。3由五核 [MoS ₄ Cu ₄ ] ^{2+ 构成}单元和 dpa 配体，与1同构。1和2之间的结构差异应该来自合成过程中[WS ₄ Cu _x ] ^{x -2}单元的异构化，我们发现温度比其他因素重要得多，如溶剂、卤化物阴离子Cu ^I盐和 [NH ₄ ] ₂ WS ₄与 Cu ^I盐的比例，用于 [WS ₄ Cu _x ] ^{x -2}单元在1和2形成中的异构化.