Syntheses, structures and properties of four 3D microporous lanthanide coordination polymers based on 3,5-pyrazoledicarboxylate and oxalate ligands

Syntheses, structures and properties of four 3D microporous lanthanide coordination polymers based on 3,5-pyrazoledicarboxylate and oxalate ligands
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四种基于3,5-吡唑二甲酸酯和草酸酯配体的3D微孔稀土配位聚合物的合成、结构和性能

DOI:
10.1016/j.jssc.2014.01.020
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发表时间:
2014-04
影响因子:
3.3
通讯作者:
Xue, Gang-Lin
Xue, Gang-Lin
中科院分区:
化学3区
文献类型:
--
作者:
Xie, Juan;Dong, Fa-Xin;Yang, Meng-Lin;Xue, Gang-Lin

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以镧系硝酸盐、3,5-吡唑二甲酸(H3 pdc)和草酸为原料,通过水热反应合成了4种具有可逆结构相互转换的三维镧系配位聚合物[Ln 2(Hpdc)2(C2 O 4)(H2O)4]n·2nH 2 O [Ln=Sm(1),Eu(2),Tb(3)和Dy(4)]。值得注意的是,1中存在原位反应,其中H3 pdc在水热条件下在Cu(II)-Sm(III)的协同作用下分解为(ox)2-。这些化合物是同构的,并且在单斜P21/c空间群中结晶。Ln(III)离子为八配位的十二面体配位构型。这些多面体通过草酸根基团连接形成一维锯齿形链,这些链进一步通过3,5-吡唑二羧酸酯连接以延伸类似的三维框架,具有沿c轴的通道1 -4。这些配位聚合物在固态下显示出Ln(III)离子的特征发射带,并具有良好的热稳定性。
Four three-dimensional lanthanide coordination polymers with reversible structural interconversions, [Ln2(Hpdc)2(C2O4)(H2O)4]n·2nH2O [Ln=Sm (1), Eu (2), Tb (3) and Dy (4)], have been synthesized by hydrothermal reactions of lanthanide nitrates with 3,5-pyrazoledicarboxylic (H3pdc) and oxalic acids. It is noteworthy that there is an in situ reaction in1, in which H3pdc was decomposed into (ox)2−with Cu(II)–Sm(III) synergistic effect under hydrothermal conditions. These compounds are isostructural and crystallized in the monoclinicP21/cspace group. TheLn(III) ions are eight-coordinated with dodecahedron coordination geometry. These polyhedra are linked by oxalate groups to form 1D zigzag chain, which are further connected by 3,5-pyrazoledicarboxylate to extend similar 3D frameworks with channels alongc-axis in1–4. These coordination polymers display the characteristic emission bands of theLn(III) ions in the solid state and possess good thermal stabilities.
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