Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur 721302, India.
Inorg Chem. 2022 Aug 8;61(31):12396-12405. doi: 10.1021/acs.inorgchem.2c01793. Epub 2022 Jul 27.
The development of chemically stable metal-organic framework (MOF)-based luminescent platforms for toxic ion detection in an aqueous medium is highly challenging because most of the classical MOFs are prone to water degradation, and that is the reason why most of the MOF-based luminescent sensors use a nonaqueous medium for sensing. In this contribution, we report two new water-stable luminescent MOFs (Zn-MOF-1 and Zn-MOF-2), assembled from a mixed-ligand synthesis approach. Because of the presence of a hydrophobic trifluoromethyl group to the backbone and stronger metal-N coordination, these MOFs exhibit excellent stability not only in water but also in acidic/alkaline aqueous solutions (pH = 3-10). Here, we report a green sensing approach by exploiting the significant reduction in photoluminescence of these MOFs in the presence of toxic ions. Fe and CrO/CrO ions could be traced with a detection limit (LOD) in the micromolar range (0.045 and 0.745/0.33 μM for Zn-MOF-1; 125.2 and 114.2/83.5 μM for Zn-MOF-2). The mechanistic study reveals that competitive absorption of the excitation energy coupled with fluorescent resonance energy transfer are responsible for the turn-off quenching. The anti-interference ability and recyclability along with the pH stability gave these MOFs high potential to be used as practical sensors toward Fe and Cr ions in water as a greenest medium.
在水相介质中开发化学稳定的金属-有机骨架(MOF)基荧光平台用于检测有毒离子极具挑战性,因为大多数经典 MOF 易于水降解,这也是大多数基于 MOF 的荧光传感器使用非水介质进行传感的原因。在本贡献中,我们报告了两种新的水稳定的发光 MOF(Zn-MOF-1 和 Zn-MOF-2),它们是通过混合配体合成方法组装而成的。由于骨架中存在疏水性三氟甲基基团和更强的金属-N 配位,这些 MOF 不仅在水中而且在酸性/碱性水溶液(pH = 3-10)中都表现出优异的稳定性。在这里,我们通过利用这些 MOF 在有毒离子存在下的光致发光显著降低来报告一种绿色传感方法。Fe 和 CrO/CrO 离子可以用微摩尔范围的检测限(LOD)追踪(对于 Zn-MOF-1,分别为 0.045 和 0.745/0.33 μM;对于 Zn-MOF-2,分别为 125.2 和 114.2/83.5 μM)。机理研究表明,激发能的竞争吸收与荧光共振能量转移相结合是导致关闭猝灭的原因。这些 MOF 具有良好的抗干扰能力、可回收性以及 pH 稳定性,使其在水作为最绿色介质中作为实用传感器对 Fe 和 Cr 离子具有很高的应用潜力。