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镧系元素-联苯-3,3'-二磺酰基-4,4'-二羧酸钾框架:气体吸附、质子传导及金属离子的发光传感

Lanthanide-Potassium Biphenyl-3,3'-disulfonyl-4,4'-dicarboxylate Frameworks: Gas Sorption, Proton Conductivity, and Luminescent Sensing of Metal Ions.

作者信息

Zhou Li-Juan, Deng Wei-Hua, Wang Yu-Ling, Xu Gang, Yin Shun-Gao, Liu Qing-Yan

机构信息

College of Chemistry and Chemical Engineering, Key Laboratory of Small Functional Organic Molecule of Ministry of Education, Jiangxi Normal University , Nanchang, Jiangxi 330022, P. R. China.

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , Fuzhou, Fujian 350002, P. R. China.

出版信息

Inorg Chem. 2016 Jun 20;55(12):6271-7. doi: 10.1021/acs.inorgchem.6b00928. Epub 2016 Jun 7.

Abstract

A novel sulfonate-carboxylate ligand of biphenyl-3,3'-disulfonyl-4,4'-dicarboxylic acid (H4-BPDSDC) and its lanthanide-organic frameworks {[LnK(BPDSDC)(DMF)(H2O)]·x(solvent)}n (JXNU-2, where JXNU denotes Jiangxi Normal University, DMF indicates dimethylformamide, and Ln = Sm(3+), Eu(3+), and Pr(3+)) were synthesized and structurally characterized. The three isomorphous lanthanide compounds feature three-dimensional frameworks constructed from one-dimensional (1D) rod-shaped heterometallic Ln-K secondary building units and are an illustration of a Kagome-like lattice with large 1D hexagonal channels and small 1D trigonal channels. The porous material of the representive JXNU-2(Sm) has an affinity to quadrupolar molecules such as CO2 and C2H2. In addition, the JXNU-2(Sm) compound exhibits humidity- and temperature-dependent proton conductivity with a large value of 1.11 × 10(-3) S cm(-1) at 80 °C and 98% relative humidity. The hydrophilic sulfonate group on the surface of channels facilitates enrichment of the solvate water molecules in the channels, which enhances the proton conductivity of this material. Moreover, the JXNU-2(Eu) material with the characteristic bright red color shows the potential for recognition of K(+) and Fe(3+) ions. The enhancing Eu(3+) luminescence with the K(+) ion and quenching Eu(3+) luminescence with the Fe(3+) ion can be associated with the functional groups of the organic ligand.

摘要

合成并表征了一种新型的联苯 - 3,3'-二磺酰基 - 4,4'-二羧酸(H4 - BPDSDC)磺酸 - 羧酸配体及其镧系有机框架{[LnK(BPDSDC)(DMF)(H2O)]·x(溶剂)}n(JXNU - 2,其中JXNU表示江西师范大学,DMF表示二甲基甲酰胺,Ln = Sm(3+)、Eu(3+)和Pr(3+))。这三种同构的镧系化合物具有由一维(1D)棒状异金属Ln - K二级结构单元构建的三维框架,是具有大的一维六边形通道和小的一维三角形通道的类 Kagome 晶格的一个实例。代表性的 JXNU - 2(Sm)多孔材料对诸如 CO2 和 C2H2 等四极分子具有亲和力。此外,JXNU - 2(Sm)化合物在 80 °C 和 98%相对湿度下表现出与湿度和温度相关的质子传导率,其值高达 1.11 × 10(-3) S cm(-1)。通道表面的亲水性磺酸基团促进了通道中溶剂化水分子的富集,从而提高了该材料的质子传导率。此外,具有特征亮红色的 JXNU - 2(Eu)材料显示出识别 K(+)和 Fe(3+)离子的潜力。K(+)离子增强 Eu(3+)发光,而 Fe(3+)离子淬灭 Eu(3+)发光,这可能与有机配体的官能团有关。

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