{Ln^III[μ₅-κ²,κ¹,κ¹,κ¹,κ¹-1,2-(CO₂)₂C₆H₄][isonicotine][H₂O]}₂Cu^I·X (Ln = Eu, Sm, Nd; X = ClO₄^-, Cl^-): A New Pillared-Layer Approach to Heterobimetallic 3d−4f 3D-Network Solids

A new series of heterometallic lanthanide(III)−copper(I) coordination polymers Ln2(bdc)2(ina)2(H2O)2Cu·X (Hina = isonicotinic acid; H2bdc = 1,2-benzenedicarboxylic acid; Ln = Eu (1), Sm (2), Nd (3), X = ClO4-; Ln = Nd (4), X = Cl-) have been hydrothermally synthesized in the presence/absence of HClO4. Both compounds are isostructural and contained two distinct units of 2D Ln−bdc layers and linear [Cu(ina)2]-. The linear [Cu(ina)2]- complexes act as pillars and further link the Ln−bdc layers resulting in four heterometallic metal−organic frameworks, which represent the first pillared-layer 3d−4f framework with two distinct types of channels along the b and c axes. The compounds can be specified by the Schläfli symbol (47·63)(47·68) as a novel 3D (5,6)-connected net. Furthermore, the IR, TGA, PXRD, and UV−vis spectral and luminescent properties of 1−4 were also studied.一系列新型异金属三价镧系-一价铜配位聚合物Ln₂(bdc)₂(ina)₂(H₂O)₂Cu·X（其中Hina为异烟酸（isonicotinic acid），H₂bdc为1,2-苯二甲酸（1,2-benzenedicarboxylic acid）；当Ln为Eu(1)、Sm(2)、Nd(3)时，X为ClO₄⁻；当Ln为Nd(4)时，X为Cl⁻），可在高氯酸（HClO₄）存在或不存在的条件下经水热合成得到。该系列化合物均为同构结构，均包含两种独立的结构基元：二维Ln-bdc层与线性[Cu(ina)₂]⁻阴离子。线性[Cu(ina)₂]⁻单元作为柱撑基团，进一步连接Ln-bdc层，最终构筑得到四种异金属有机框架（metal-organic framework）。这是首例具有沿b轴与c轴分布的两类独立孔道的柱撑层状3d-4f金属有机框架。该系列化合物可通过施莱夫利符号（Schläfli symbol）(4⁷·6³)(4⁷·6⁸)进行表征，属于一种新型三维(5,6)-连接拓扑网格。此外，本文还对化合物1~4的红外光谱、热重分析、粉末X射线衍射、紫外-可见光谱及发光性能展开了表征与研究。