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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >3D isomorphous lanthanide coordination polymers displaying magnetic refrigeration, slow magnetic relaxation and tunable proton conduction
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3D isomorphous lanthanide coordination polymers displaying magnetic refrigeration, slow magnetic relaxation and tunable proton conduction

机译：3D同构镧系元素配位聚合物显示磁制冷，慢磁性松弛和可调质子传导

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Four new isostructural lanthanide-based three-dimensional (3D) coordination polymers (CPs), {[Ln(4)(OH)(4)(L)(2)(H2O)(8)]4.6H(2)O1.4CH(3)CN}(n) (Ln(3+) = Gd3+ (1), Dy3+ (2), Ho3+ (3) and Er3+ (4)), have been constructed using a sulfonate-carboxylate-based ligand (Na2H2L = disodium-2,2-disulfonate-4,4-oxydibenzoic acid) and the corresponding lanthanide metal(iii) nitrates. All the CPs 1-4 contain [Ln(4)((3)-OH)(4)](8+) cubane-like cores interconnected through L4- ligands to give rise to 3D coordination frameworks with 1D hydrophilic channels along the crystallographic c direction. From the topological perspective, the underlying 3D nets of the CPs can be classified as a 3,6,6-c net with an undocumented topology. Magnetic studies display that CP 1 exhibits a magnetocaloric effect with a significant magnetic entropy change (-S-m) = 34.6 J kg(-1) K-1 for H = 7 T at 3 K. CP 2 shows field-induced slow magnetic relaxation properties with energy barrier (U-eff/k(B)) = 30.40 K and relaxation time ((0)) = 2.47 x 10(-7) s. Theoretical calculations have been performed to corroborate the magnetic exchange coupling constant value for CP 1 and to obtain a deeper understanding of the field-induced slow magnetic relaxation behavior of CP 2. Impedance analyses display high values of proton conductivity which reach 2.02 x 10(-6), 2.96 x 10(-6), 4.56 x 10(-3) and 6.59 x 10(-3) S cm(-1) for CPs 1-4, respectively at high temperature (75 degrees C) and 95% relative humidity (RH) in the order CP 1 CP 2 CP 3 CP 4. Notably, the proton conductivities for CPs 3 and 4 are a few orders of magnitude higher than those of CPs 1 and 2 (10(-3) S cm(-1)vs. 10(-6) S cm(-1)), and the conductivity increases periodically following the decreasing order of ionic radius (Gd3+ Dy3+ Ho3+ Er3+). This demonstrates the effective employment of the lanthanide contraction strategy to tune proton conductivity while preserving proton-conducting pathways.
机译：四种新的基于Isostrontuctoral镧三维（3D）配位聚合物（CPS），{[LN（4）（OH）（4）（4）（2）（2）（H 2 O）（8））] 4.6H（2）o1。使用磺酸盐 - 羧酸盐的配体（Na 2 H 2L，4CH（3）CN}（N）（LN（3+）= Gd3 +（1），DY3 +（2），HO3 +（3）和ER3 +（4））已构建=二钠-2,2-二磺酸-4,4-羟基苯甲酸）和相应的镧系金属（III）硝酸盐。所有CPS 1-4含有[LN（4）（（3）-OH）（4）]（4）型）（8 +）邻接通过L4-配体的核心，以产生沿着晶体的1D亲水通道的3D配位框架C方向。从拓扑角度来看，CPS的底层3D网可以被归类为具有无证拓扑的3,6,6-C网。磁性研究显示CP 1在3k = 7T的情况下表现出具有显着磁熵变化（-SM）= 34.6Jkg（-1）K-1的磁热效应.CC 2显示了场诱导的慢磁性弛豫特性具有能量屏障（U-Eff / K（B））= 30.40 k和弛豫时间（（0））= 2.47 x 10（-7）s。已经进行了理论计算以证实CP 1的磁交换耦合恒定值，并获得对CP的现场诱导的慢磁松弛行为的更深理解。阻抗分析显示达到2.02×10的质子电导率的高值（ - 6），在高温（＆ 75℃）和4.56×10（-3），4.56×10（-3），4.56×10（-3）和6.59×10（-3）厘米（-1），订单CP 1中的95％相对湿度（RH）1＆ CP 2＆ CP 3＆ CP 4.值得注意的是，CPS 3和4的质子电导率是高于CPS 1和2（10（-3）CM（-1）Vs的数量级的数量级。10（-6）Scm（ - 1）），电导率在离子半径的降低（Gd3 +＆ Dy3 +＆ HO3 +＆ ER3 +）上周期性地增加。这证明了镧系元素收缩策略的有效采用质子电导率，同时保持质子导电途径。

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