一例新型船式九核锰簇的构筑和溶液行为研究

Construction and Solution Behavior Study of a Novel Boat-Like Nonanuclear Manganese Cluster

为了实现定向设计和组装高核配合物,探究多核配合物的形成过程。在溶剂热条件下选择双齿苯并咪唑醇配体(^(1)H-2-苯并咪唑基-2-甲基-1,3-丙二醇,H_(2)L)与Mn(ClO_(4))_(2)·6H_(2)O“一锅法”合成一例九核Mn簇,即[Mn_(5)^(II)Mn_(4)^(IV)(L)_(2)(L′)_(4)(HCOO)_(6)(CH_(3)O)_(3)(OH)·3CH_(3)OH·2H_(2)O(Mn9)。Mn9的核心骨架可以看作是由一个Mn金属中心连接两个立方烷Mn_(4)O_(4)核单元形成的一个类似船型的新型结构。重要的是,化合物Mn9的形成过程是由[Mn_(4)L′_(2)L]和[Mn_(5)L′_(2)L]两个片段组成,这一点分别被粉末X射线衍射和电喷雾质谱所提供的固体和溶液信息所证实。此外,化合物Mn9结构磁性行为显示其Mn金属离子间反铁磁相互作用主导。

In order to realize the directional design and assembly of high-core complexes,the formation process of multinuclear complexes is explored.A nonanuclear manganese cluster was synthesized under solvent-heated conditions based on a bidentate benzimidazole alcohol ligand(^(1)H-2-benzimidazolyl-2-methyl-1,3-propanediol,H_(2)L)with Mn(ClO_(4))_(2)·6H_(2)O in a"one-pot"method,namely[Mn_(5)^(II)Mn_(4)^(IV)(L)_(2)(L')_(4)(HCOO)_(6)(CH_(3)O)_(3)(OH)·3CH_(3)OH·2H_(2)O(Mn9).The core skeleton of compound Mn9 can be viewed as a novel ship-like structure formed by a Mn metal center connected to two cubane Mn 4O 4 nuclear units.Importantly,the formation process of compound Mn9 consists of two fragments,[Mn_(4)L'_(2)L]and[Mn_(5)L'_(2)L],as confirmed by solid and solution information provided by powder X-ray diffraction and electrospray mass spectrometry.Moreover,the magnetic behavior of the compound Mn9 structure shows that its antiferromagnetic interactions between Mn metal ions dominate.