unctionalization of Microporous Lanthanide-Based Metal-Organic Frameworks by Dicarboxylate Ligands with Methyl-Substituted Thieno[2,3-b]thiophene Groups: Sensing Activities and Magnetic Properties
unctionalization of Microporous Lanthanide-Based Metal-Organic Frameworks by Dicarboxylate Ligands with Methyl-Substituted Thieno[2,3-b]thiophene Groups: Sensing Activities and Magnetic Properties
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具有甲基取代的噻吩并[2,3-b]噻吩基团的二羧酸配体对微孔镧系金属有机框架的官能化：传感活性和磁性
DOI：
10.1021/acs.inorgchem.5b02801
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发表时间：
2016
影响因子：
4.6
通讯作者：
Bai Junfeng
中科院分区：
文献类型：
--
作者：
Wang Suna;Cao Tingting;Yang Hui;Li Yunwu;Lu Jing;Ma Ranran;Li Dacheng;Dou Jianmin;Bai Junfeng
从甲基取代的[2，3-b]噻吩二甲酸酯出发，合成了三种三维微孔稀土金属有机骨架：{[Ln(DMTDC)1.5(H2O)2]·DEF}n(类型I，Ln=Eu1，Tb2)，{[Ln(DMTDC)1.5(H2O)2]·0.5DMF·0.5H2O}n(类型II，Ln=Gd3，DY4，Er5)和{[Ln4(DMTDC)6(DMF)2]·0.5DMF·1.5H2O}n(类型III，Ln=Er6)(H_2DMTDC=3，4-dimethylthieno[2，3-b]thiophene-2，5-dicarboxylic酸，DEF=N，N‘-二甲基甲酰胺，DMF=N，N’-二甲基甲酰胺)。类型I和类型II是等结构的，它们呈现由双链杆状{Ln(CO2)2}核链构成的一维三角形沟道。类型III显示了一个有趣的骨架，它具有沿(1，1，0)和(1，-1，0)轴排列的三链杆状{Ln(CO2)3}nchain，并沿两个轴分别具有两种三角形通道。噻吩基的Lewis碱位的固定化诱导气体吸附和传感性能进入这些微孔骨架。配合物5(Er)和6(Er)对N_2和CO_2表现出中等的吸附性能，CO_2的Qst分别高达36.3和34.8kJ·mol~(-1)。配合物1(Eu)和2(Tb)在DMF和水溶液中都表现出对硝基苯、丙酮和Cu2+离子的传感性能。络合物3(Gd)在3.0K和7T下表现出明显的磁热效应，ΔSm=24.3J·kg-1·K-1。络合物4(Dy)表现出缓慢的磁弛豫，其势垒Δ/kB值为48.29K。
From a methyl-substituted thieno[2,3-b]thiophene dicarboxylate, three types of three-dimensional (3-D) microporous lanthanide-based metal–organic frameworks, {[Ln(DMTDC)1.5(H2O)2]·DEF}n(type I, Ln = Eu1, Tb2), {[Ln(DMTDC)1.5(H2O)2]·0.5DMF·0.5H2O}n(type II, Ln = Gd3, Dy4, Er5), and {[Ln4(DMTDC)6(DMF)2]·0.5DMF·1.5H2O}n(type III, Ln = Er6) (H2DMTDC = 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid, DEF =N,N′-diethylformamide, DMF =N,N′-dimethylformamide), have been solventhermally synthesized. TypesIandIIare isostructural, which exhibit 1-D triangular channels constructed by double-stranded rod-shaped {Ln(CO2)2}nchains. TypeIIIdemonstrates an intriguing framework with triple-stranded rod-shaped {Ln(CO2)3}nchains arranged along the (1,1,0) and (1,–1,0) axes and possesses two kinds of triangular channels along two axes, respectively. Immobilization of the Lewis basic sites of thiophene groups induced gas adsorption and sensing properties into these microporous frameworks. Complexes5(Er)and6(Er)display moderate adsorption properties toward N2and CO2, and theQstof CO2are as high as 36.3 and 34.8 kJ mol–1, respectively. Complexes1(Eu)and2(Tb)exhibit sensing properties toward nitrobenzene, acetone, and the Cu2+ion in both DMF and aqueous solution. Complex3(Gd)shows a significant magnetocaloric effect with ΔSm= 24.3 J·kg–1·K–1at 3.0 K and 7 T. Complex4(Dy)exhibits slow magnetic relaxation with the energy barrier Δ/kBof 48.29 K.