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二钌三价碳酸镉展示出不同的磁学行为,这源于[Ru2(CO3)4]n(3n-)层的不同构型。

Cadmium diruthenium(II,III) carbonates showing diverse magnetism behavior arising from variety configuration of [Ru2(CO3)4]n(3n-) layer.

机构信息

Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710069, P. R. China.

出版信息

Dalton Trans. 2013 Jul 28;42(28):10208-13. doi: 10.1039/c3dt51143j.

Abstract

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.

摘要

两种异金属碳酸盐,即 KCd(H2O)3Ru2(CO3)4·4H2O(1)和 KCd(H2O)3Ru2(CO3)4·3.5H2O(2),在中性水溶液中合成。这两个 3D 维结构的配合物都包含混合价双钌(II,III)碳酸桨轮核 Ru2(II,III)(CO3)4(3-),它们通过碳酸氧原子以反式或顺式模式相互连接,分别形成矩形正方形网格和异构平行四边形层[Ru2(CO3)4]n(3n-)在 1 和 2 中。反应温度被发现对指导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-)单元之间的各种连接模式。磁性研究表明,在两个配合物 1 和 2 中,双钌单元之间存在铁磁相互作用,但它们的磁性在低温下有所不同,其中反式连接模式平行四边形层[Ru2(CO3)4]n(3n-)在 2 中导致在 4.0 K 以下的远程磁序。然而,对于包含顺式模式异构矩形正方形网格连接的配合物 1,在 1.8 K 以下没有检测到居里有序。

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