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以四碳酸二钌片段和镧系(III)离子为构建单元构建二维配位聚合物

Tetracarbonatodiruthenium Fragments and Lanthanide(III) Ions as Building Blocks to Construct 2D Coordination Polymers.

作者信息

Gutiérrez-Martín Daniel, Cortijo Miguel, Martín-Humanes Álvaro, González-Prieto Rodrigo, Delgado-Martínez Patricia, Herrero Santiago, Priego José L, Jiménez-Aparicio Reyes

机构信息

Departamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Ciudad Universitaria, E-28040 Madrid, Spain.

Centro de Asistencia a la Investigación Difracción de Rayos X, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, E-28040 Madrid, Spain.

出版信息

Polymers (Basel). 2019 Mar 5;11(3):426. doi: 10.3390/polym11030426.

Abstract

Two-dimensional coordination polymers of [Pr(DMSO)₂(OH₂)₃][Ru₂(CO₃)₄(DMSO)(OH₂)]·5H₂O () and [Ln(OH₂)₅][Ru₂(CO₃)₄(DMSO)]·H₂O (Ln = Sm (), Gd ()) formulae have been obtained by reaction of the corresponding Ln(NO₃)₃·6H₂O dissolved in dimethyl sulphoxide (DMSO) and K₃[Ru₂(CO₃)₄]·4H₂O dissolved in water. Some DMSO molecules are coordinated to the metal atoms reducing the possibilities of connection between the [Ru₂(CO₃)₄] and Ln building blocks giving rise to the formation of two-dimensional networks. The size of the Ln ion and the synthetic method seem to have an important influence in the type of two-dimensional structure obtained. Slow diffusion of the reagents gives rise to that forms a 2D net that is built by Ln ions as triconnected nodes and two types of Ru₂ units as bi- and tetraconnected nodes with (2-c)(3-c)₂(4-c) stoichiometry (α structure). An analogous synthetic procedure gives and that display a grid-like structure, (2-c)₂(4-c)₂, formed by biconnected Ln ions and two types of tetraconnected Ru₂ fragments (β structure). The magnetic properties of these compounds are basically explained as the sum of the individual contributions of diruthenium and lanthanide species, although canted ferrimagnetism or weak ferromagnetism are observed at low temperature.

摘要

通过将溶解于二甲基亚砜(DMSO)中的相应Ln(NO₃)₃·6H₂O与溶解于水中的K₃[Ru₂(CO₃)₄]·4H₂O反应,得到了化学式为[Pr(DMSO)₂(OH₂)₃][Ru₂(CO₃)₄(DMSO)(OH₂)]·5H₂O()和[Ln(OH₂)₅][Ru₂(CO₃)₄(DMSO)]·H₂O(Ln = Sm(),Gd())的二维配位聚合物。一些DMSO分子与金属原子配位,降低了[Ru₂(CO₃)₄]与Ln结构单元之间连接的可能性,从而形成二维网络。Ln离子的大小和合成方法似乎对所获得的二维结构类型有重要影响。试剂的缓慢扩散产生了,其形成了一个二维网络,该网络由作为三连接节点的Ln离子和两种类型的作为双连接和四连接节点的Ru₂单元以(2 - c)(3 - c)₂(4 - c)化学计量比构建而成(α结构)。类似的合成过程得到了和,它们呈现出由双连接的Ln离子和两种类型的四连接Ru₂片段形成的网格状结构,(2 - c)₂(4 - c)₂(β结构)。这些化合物的磁性基本上可以解释为二钌和镧系物种各自贡献的总和,尽管在低温下观察到了倾斜亚铁磁性或弱铁磁性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ea30/6473724/bbcb856e1dca/polymers-11-00426-g001.jpg

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