A Rational Route to Coordination Polymers with Condensed Networks and Cooperative Magnetic Properties
A Rational Route to Coordination Polymers with Condensed Networks and Cooperative Magnetic Properties
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DOI：
10.1002/zaac.201300274
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发表时间：
2013-12
期刊：
影响因子：
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通讯作者：
C. Näther;S. Wöhlert;J. Boeckmann;Mario Wriedt;I. Jess
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文献类型：
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作者：
C. Näther;S. Wöhlert;J. Boeckmann;Mario Wriedt;I. Jess
本文提出了一条合成具有协同磁性的配位聚合物的合理途径。在该方法中，加热基于过渡金属阳离子、小尺寸末端N-键合阴离子配体和另外的中性N-供体共配体的化合物，这导致中间体的形成，其中金属阳离子通过阴离子配体连接。主要是，使用这种方法的桥接硫代和硒氰配合物的合成在这篇文章中描述，但它也可以扩展到其他化合物的制备。在大多数情况下，中间体以非常纯的形式和定量产率形成。因此，如果在溶液中进行合成，则可以制备不获得或至少非常难以获得的化合物。这对于硫代和硒代氰基配位化合物尤其有效，其大多优选末端键合而不是与较少亲铜金属阳离子如Mn II、Fe II、Co II或Ni II的桥接配位。它演示了如何1D和2D网络可以选择性地制备，这种方法是predestinated用于合成的化合物，表现出缓慢的弛豫的磁化。大量的化合物进行了研究，其中金属阳离子，阴离子配体，或中性共配体交换，这使得结构-性能关系的研究。进一步的研究表明，这些反应可以通过几种不同的中间体进行。乍一看，这种方法的一个缺点可能是分离的中间体由微晶粉末组成，其结构难以表征。然而，提出了不同的可能性，以克服这个问题，包括调查的类似化合物的基础上的抗磁性镉阳离子，这与顺磁性金属阳离子更喜欢的阴离子配体的桥接配位。
In this report a rational route to coordination polymers that can show cooperative magnetic phenomena is presented. In this approach compounds based on transition metal cations, small sized terminal N-bonded anionic ligands and additional neutral N-donor co-ligands are heated, which lead to the formation of intermediates, in which the metal cations are linked by the anionic ligands. Predominantly, the use of this method for the synthesis of bridged thio- and selenocyanato coordination compounds is described in this article but it can also be extended for the preparation of other compounds. In most cases the intermediates are formed in very pure form and in quantitative yields. Thus, compounds, which are not or at least very difficult to obtain, can be prepared if the synthesis is performed in solution. This is especially valid for thio- and selenocyanato coordination compounds, which mostly prefer terminal bonding instead of bridging coordination with less chalcophilic metal cations like e.g. MnII, FeII, CoII, or NiII. It is demonstrated how 1D and 2D networks can selectively be prepared and that this method is predestinated for the synthesis of compounds that show a slow relaxation of the magnetization. A large number of compounds were investigated in which the metal cation, the anionic ligand, or the neutral co-ligand is exchanged, which allowed the study of structure-property relationships. Further investigation showed that these reactions can proceed via several different intermediates. At first glance one disadvantage of this approach might be that the intermediates isolated consist of microcrystalline powders, which structurally are difficult to characterize. However, different possibilities are presented to overcome this problem including investigations of analogous compounds based on diamagnetic cadmium cations, which in contrast to the paramagnetic metal cations prefer a bridging coordination of the anionic ligands.