Cadmium diruthenium(II,III) carbonates showing diverse magnetism behavior arising from variety configuration of [Ru2(CO3)4]n(3n-) layer.
Cadmium diruthenium(II,III) carbonates showing diverse magnetism behavior arising from variety configuration of [Ru2(CO3)4]n(3n-) layer.
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DOI：
10.1039/c3dt51143j
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发表时间：
2013-06
影响因子：
4
通讯作者：
Bin Liu;Yan-Yan Jia-Yan;Jin Jin-Jin;Xuemei Liu;Dan Wang;G. Xue
中科院分区：
文献类型：
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作者：
Bin Liu;Yan-Yan Jia-Yan;Jin Jin-Jin;Xuemei Liu;Dan Wang;G. Xue
在中性水溶液中合成了KCd(H2O)3Ru2(CO3)4·4H2O(1)和KCd(H2O)3Ru2(CO3)4·3.5H2O(2)两种杂金属碳酸盐。这两种三维结构配合物均含有Ru2(II，III)(CO3)4（3-）的混价碳酸二钌（II，III）桨轮核，它们通过碳酸盐氧原子以反式或顺式模式相互连接，分别在1和2上形成矩形方形网格和异构平行四边形层[Ru2(CO3)4]n（3n-）。研究发现，反应温度对具有特定拓扑结构的最终产物起着重要作用，其层状结构的多样性是由于Ru2(CO3)4（3-）单元之间的不同连接模式所致。磁性研究表明，配合物1和配合物2中的二钌单元之间存在铁磁相互作用，但在低温下它们的磁性不同，其中配合物2中的反联模式平行四边形层[Ru2(CO3)4]n（3n-）导致4.0 K以下的远程磁有序。然而，对于包含以顺式模式连接的同分异构体矩形方格网格层的复合体1，没有检测到低于1.8 K的居里序。
Two hetero-metallic carbonates, namely KCd(H2O)3Ru2(CO3)4·4H2O (1) and KCd(H2O)3Ru2(CO3)4·3.5H2O (2), have been synthesized in a neutral aqueous solution. Both of the 3D dimensional structured complexes contain mixed-valent diruthenium(II,III) carbonate paddlewheel cores of Ru2(II,III)(CO3)4(3-) that are connected to each other in trans- or cis-modes by carbonate oxygen atoms, forming rectangular square-grid and isomeric parallelogram layers [Ru2(CO3)4]n(3n-) in 1 and 2, respectively. The reaction temperature is found to play an important role in directing the final products with particular topologies and their layered structural diversity is due to the various linking modes between the Ru2(CO3)4(3-) units. The magnetic studies show that ferromagnetic interactions are propagated between the diruthenium units in both complexes 1 and 2 but their magnetic properties differ at low temperatures, in which the trans linking mode parallelogram layer [Ru2(CO3)4]n(3n-) in complex 2 leads to long-range magnetic ordering below 4.0 K. However, no Curie ordering down to 1.8 K is detected for complex 1 containing the isomeric rectangle square-grid layer linking in the cis mode.