A reductive-aggregation route to [Mn12O12(OMe)2(O2CPh)16(H2O)2]2- single-molecule magnets related to the [Mn12] family.
A reductive-aggregation route to [Mn12O12(OMe)2(O2CPh)16(H2O)2]2- single-molecule magnets related to the [Mn12] family.
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DOI：
10.1002/anie.200461551
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发表时间：
2004-11
影响因子：
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通讯作者：
A. Tasiopoulos;W. Wernsdorfer;K. Abboud;G. Christou
中科院分区：
文献类型：
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作者：
A. Tasiopoulos;W. Wernsdorfer;K. Abboud;G. Christou
配合物2a [12]属于正交晶系，空间群为Pbca，其不对称单元含有一半的[Mnо12] 2 π团簇和一个[NnBu 4]+离子，以及一个H2O和两个无序的CH 2Cl 2溶剂分子。2a的[Mnо12] 2 π离子（图1）含有一个中心[MnIV 4（μ3-O）2（μ-O）2（μ-OMe）2] 6+单元，该单元被一个由八个Mn III原子组成的非平面环包围，这些Mn III原子通过八个桥接μ3-O2 π离子连接到中心Mn 4单元。金属的氧化态和它们的捕获价性质是通过检查MnO 2 O键长、锰键价和计算[13]以及外环中锰原子的MnIII Jahn-Teller伸长轴的存在来确定的。外Mn 8环与正常[Mn 12]化合物1非常相似，但1具有中心[Mn 4（μ3-O）4] 8+立方烷。中央[MnIV]
Complex 2a [12] crystallizes in the orthorhombic space group Pbca with its asymmetric unit containing half the [Mnо12] 2Àcluster and one [NnBu4]+ ion, as well as one H2O and two disordered CH2Cl2 solvent molecules. The [Mnо12] 2À ion of 2a (Figure1) contains a central [MnIV 4 (μ3-O) 2 (μ-O) 2 (μ-OMe) 2] 6+ unit surrounded by a nonplanar ring of eight MnIII atoms that are connected to the central Mn4 unit by eight bridging μ3-O2À ions. The metal oxidation states and their trapped-valence nature were determined by inspection of the MnÀO bond lengths, manganese bond valence sum calculations,[13] and the presence of MnIII Jahn–Teller elongation axes for the manganese atoms in the outer ring. The outer Mn8 ring is very similar to that in normal [Mn12] compound 1, but 1 has a central [Mn4 (μ3-O) 4] 8+ cubane. The central [MnIV