Four series of lanthanide coordination polymers based on the tetrabromobenzene-1,4-dicarboxylate ligand: structural diversity and multifunctional properties
Four series of lanthanide coordination polymers based on the tetrabromobenzene-1,4-dicarboxylate ligand: structural diversity and multifunctional properties
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基于四溴苯-1,4-二羧酸酯配体的四个系列镧系配位聚合物：结构多样性和多功能特性
DOI：
10.1039/d2dt00007e
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发表时间：
2022
影响因子：
4
通讯作者：
Chainok Kittipong
中科院分区：
文献类型：
--
作者：
Jiajaroen Suwadee;Dungkaew Winya;Kielar Filip;Sukwattanasinitt Mongkol;Sahasithiwat Somboon;Zenno Hikaru;Hayami Shinya;Azam Mohammad;Al-Resayes Saud I.;Chainok Kittipong
合成了四个系列的镧系配位聚合物[Ln（Br 4 bdc）1.5（MeOH）3]（1Ln; Ln = Ce，Pr，Nd，Sm，Eu，Gd，Tb，Dy），[Ln2（Br4bdc）2（NO3）2（MeOH）4]（2Ln; Ln = Ce，Pr，Nd，Sm），[Ln（Br4bdc）（NO3）（MeOH）]（3Ln; Ln = Gd，Tb，Dy）和[Ln2（Br4bdc）3（H2O）2.3（MeOH）2.7]在溶剂热条件下，用水合稀土盐与四溴苯-1，4-二甲酸（H_2Br_4bdc）在不同溶剂中反应，合成了（4Ln; Ln = Gd，Tb，Dy）。在该体系中发现的结构多样性主要是由于阴离子，溶剂，和镧系元素（III）离子的离子半径的变化的影响。系列1 Ln中的化合物特征在于具有基于{（Ln（COO）2）2（μ-COO）2}二级结构单元（SBU）的sql拓扑的二维（2D）层状结构。系列2Ln和3Ln中的化合物分别包含{Ln（COO）2} nSBU的无限均匀和交替链，其组装成与1 Ln类似的网络拓扑。同时，系列化合物4Ln具有由双核{Ln 2（COO）3} SBU组成的pcu α-Po拓扑网络的三维配位网络。1 Ln-4Ln系列聚合物网络的形成是由配体Br 4 bdc 2 −的大量配位位点以及其溴原子可以参与形成各种类型的分子间相互作用的事实促进的。对含Eu-（1 Eu）和Tb-（1 Tb，3 Tb，4 Tb）化合物的固态光致发光研究表明，Br 4 bdc 2 −配体能有效敏化Eu 3+和Tb 3+的发光。值得注意的是，此类化合物通过荧光猝灭效应对丙酮、水和Fe 3+离子表现出高度灵敏的荧光感测。作为该系列的代表，活化的1 Eu、2 Pr、3 Tb和4 Tb在50 bar和298 K下分别显示出170.4、273.7、255.3和303.5 cm 3 g-1的最大CO2吸收容量，具有良好的吸附-解吸性质的重复性。磁性研究表明，Gd和Dy基化合物1Gd，1Dy，3Gd，3Dy，和4Gd显示简单的顺磁性行为，而化合物4Dy表现出弱的铁磁相互作用。
Four series of lanthanide-based coordination polymers (LnCPs), namely [Ln(Br4bdc)1.5(MeOH)3] (1Ln; Ln = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy), [Ln2(Br4bdc)2(NO3)2(MeOH)4] (2Ln; Ln = Ce, Pr, Nd, Sm), [Ln(Br4bdc)(NO3)(MeOH)] (3Ln; Ln = Gd, Tb, Dy), and [Ln2(Br4bdc)3(H2O)2.3(MeOH)2.7] (4Ln; Ln = Gd, Tb, Dy) have been synthesized by reacting hydrated lanthanide(III) salts with tetrabromobenzene-1,4-dicarboxylic acid (H2Br4bdc) in different solvents under solvothermal conditions. The structural diversity found in the system mainly resulted from the effects of anions, solvents, and the variation in the ionic radii of the lanthanide(III) ions. Compounds in series 1Ln feature a two-dimensional (2D) layered structure with sql topology based on {(Ln(COO)2)2(μ-COO)2} secondary building units (SBUs). Compounds in series 2Ln and 3Ln comprise, respectively, infinite uniform and alternate chains of {Ln(COO)2}n SBUs that are assembled into a similar network topology to 1Ln. Meanwhile, compounds in series 4Ln feature 3D coordination networks of a pcu α-Po topological net consisting of binuclear {Ln2(COO)3} SBUs. The formation of polymeric networks in series 1Ln–4Ln is facilitated by the numerous coordination sites of the ligand Br4bdc2− and the fact that its bromine atoms can participate in the formation of various types of intermolecular interactions. The solid-state photoluminescence studies on Eu- (1Eu) and Tb- (1Tb, 3Tb, 4Tb) containing compounds indicate that the Br4bdc2− ligands can efficiently sensitize Eu3+ and Tb3+ emission. Notably, such compounds exhibit highly sensitive fluorescence sensing for acetone, water, and Fe3+ ions via the fluorescence quenching effect. As the representatives of the series, activated 1Eu, 2Pr, 3Tb, and 4Tb show the maximum CO2 uptake capacities of 170.4, 273.7, 255.3, and 303.5 cm3 g−1, respectively, at 50 bar and 298 K with good repeatability of the adsorption–desorption properties. Magnetic studies indicate that the Gd- and Dy-based compounds 1Gd, 1Dy, 3Gd, 3Dy, and 4Gd show simple paramagnetic behaviours, whereas compound 4Dy exhibits weak ferromagnetic interactions.