Zhou Ya-Nan, Zhao Si-Jia, Leng Wen-Xing, Zhang Xu, Liu Dong-Yan, Zhang Jia-Hui, Sun Zhen-Gang, Zhu Yan-Yu, Zheng Han-Wen, Jiao Cheng-Qi
School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, P. R. China.
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, P. R. China.
Inorg Chem. 2023 Aug 14;62(32):12730-12740. doi: 10.1021/acs.inorgchem.3c01224. Epub 2023 Aug 2.
The construction of attractive dual-functional lanthanide-based metal-organic frameworks (Ln-MOFs) with ratiometric fluorescent detection and proton conductivity is significant and challenging. Herein, a three-dimensional (3D) , namely, [Eu(HL)(SBA)(HO)]·9HO, has been hydrothermally synthesized with a dual-ligand strategy, using (4-carboxypiperidyl)--methylenephosphonic acid (HL = HOPCH-NCH-COOH) and 4-sulfobenzoic acid monopotassium salt (KHSBA = KOSCHCOOH) as organic linkers. showed ratiometric fluorescent broad-spectrum sensing of benzophenone-like ultraviolet filters (BP-like UVFs) with satisfactory sensitivity, selectivity, and low limits of detection in water/ethanol (1:1, v/v) solutions and real urine systems. A portable test paper was prepared for the convenience of actual detection. The potential sensing mechanisms were thoroughly analyzed by diversified experiments. The synergistic effect of the forbidden energy transfer from the ligand to Eu, the internal filtration effect (IFE), the formation of a complex, and weak interactions between the KHSBA ligand and BP-like UVFs is responsible for the ratiometric sensing effect. Meanwhile, displayed relatively high proton conductivity of 2.60 × 10 S cm at 368 K and 95% relative humidity (RH), making it a potential material for proton conduction. This work provides valuable guidance for the facile and effective design and construction of multifunctional Ln-MOFs with promising performance.
构建具有比率荧光检测和质子传导功能的有吸引力的双功能镧系金属有机框架(Ln-MOFs)具有重要意义且具有挑战性。在此,采用双配体策略,以(4-羧基哌啶基)-亚甲基膦酸(HL = HOPCH₂-NCH₂COOH)和4-磺基苯甲酸钾盐(KHSBA = KOSCH₂COOH)作为有机连接体,水热合成了一种三维(3D)的[Eu(HL)(SBA)(H₂O)]·9H₂O。其在水/乙醇(1:1,v/v)溶液和实际尿液系统中对二苯甲酮类紫外线过滤剂(BP类UVFs)表现出比率荧光广谱传感,具有令人满意的灵敏度、选择性和低检测限。为方便实际检测制备了便携式试纸。通过多种实验对潜在的传感机制进行了深入分析。从配体到Eu的禁戒能量转移、内滤效应(IFE)、复合物的形成以及KHSBA配体与BP类UVFs之间的弱相互作用的协同效应导致了比率传感效应。同时,其在368 K和95%相对湿度(RH)下显示出相对较高的质子传导率2.60×10⁻⁴ S cm⁻¹,使其成为一种潜在的质子传导材料。这项工作为简便有效地设计和构建具有优异性能的多功能Ln-MOFs提供了有价值的指导。