From an organic-functionalized Ge4S6 cage to a chalcogenidometallate organic coordination framework with antiferromagnetic chain behavior.
From an organic-functionalized Ge4S6 cage to a chalcogenidometallate organic coordination framework with antiferromagnetic chain behavior.
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从有机功能化的 Ge4S6 笼到具有反铁磁链行为的硫族金属盐有机配位框架
作者：
Z. Hassanzadeh Fard;R. Clerac;S. Dehnen
对含有硫属化物结构单元的开放骨架化合物的兴趣是由于孔隙率与硫属化物部分的其它特定化学或物理性质的固有组合。[1-7]到目前为止，已经引入了三种不同类型的这些化合物，其中硫属金属化物络合物或簇1）通过硫属配体连接，如在基于[Cu 5In 30 S54] 13 π簇的开放框架中，[8] 2）通过金属离子连接，如在[Sn（Zn 4Sn 4S 17）] 6S，[9]或3）通过配位胺如[Zn 8 SACTUNGTRENNUNG（SC 6 H5）14·C13 H14 N2]中。[10]最后一组代表无机-有机混合框架，其将有机连接体的特性（例如柔性、手性或进一步的供体/受体能力）添加到金属硫族化物片段的特性（例如光电性质或磁性）中。基于我们最近报道的有机官能化硫族金属化物络合物的定向合成，[11，[12]我们提出了一类新的无机-有机杂化化合物，其中无机硫族金属化物笼（Ge 4S 6）与供体基团（COOH 4）共价键合在有机配体的末端，通过过渡金属离子（Mn 2+）的配位连接。通过四取代丙酸取代的金刚烷型硫代锗酸盐（HOOCC 2 H4 Ge）4S 6反应，合成了硫代锗酸盐有机配位骨架[Mn 2 {（OOCC 2 H4 Ge）4S 6} ACHTUNGTRENNUNG（MeOH）ACHTUNGTRENNUNG（dmf）2]（1
The interest in open framework compounds containing chalcogenide building units is due to the intrinsic combination of porosity with further specific chemical or physical properties of the chalcogenide moiety.[1–7] To date, three different classes of these compounds have been introduced in which chalcogenidometallate complexes or clusters are linked 1) by chalcogenide ligands as in the open framework based on [Cu5In30S54] 13À clusters,[8] 2) by metal ions as observed in [Sn (Zn4Sn4S17)] 6À,[9] or 3) by coordinating amines as in [Zn8SACHTUNGTRENNUNG (SC6H5) 14· C13H14N2].[10] The last group represent inorganic–organic hybrid frameworks that add the peculiarities of an organic linker—such as flexibility, chirality or further donor/acceptor capabilities—to the characteristics of the metal chalcogenide fragment—such as optoelectronic properties or magnetism.Based on the directed synthesis of organic-functionalized chalcogenidometallate complexes, which we have reported very recently,[11, 12] we present a new class of inorganic–organic hybrid compounds, in which inorganic chalcogenidometallate cages (Ge4S6) with donor groups (COOÀ) at covalently bonded terminal organic ligands are linked by the coordination of transition-metal ions (Mn2+). The thiogermanate organic coordination framework,[Mn2 {(OOCC2H4Ge) 4S6} ACHTUNGTRENNUNG (MeOH) ACHTUNGTRENNUNG (dmf) 2](1), was synthesized by reaction of the fourfold propionic acid substituted adamantane-type thiogermanate(HOOCC2H4Ge) 4S6
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