Sulfur-hinged L-shaped ligand-based Cd(ii)–organic framework: a fluorescent tool for targeting environmental nitroaromatics†

IF 2.6 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
CrystEngComm Pub Date : 2024-11-01 DOI:10.1039/D4CE01050G
Nitu Rani, Aman K. K. Bhasin, Ahmad Husain, Annu Kumari, Reshu Verma, K. K. Bhasin and Girijesh Kumar
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Abstract

We present the synthesis and detailed structural characterization of a cadmium-based metal–organic framework (Cd-MOF) with the formula [Cd(L4-Py)(nipa)(H2O)]n, where L4-Py stands for N,N′-(thiobis(4,1-phenylene))diisonicotinamide and anionic nipa2− represents 5-nitroisophthalate. This Cd-MOF has been investigated for its potential application as a fluorescent probe, demonstrating highly selective recognition of nitroaromatic compounds (NACs). The Cd-MOF was synthesized using ligand L4-Py, co-ligand H2nipa, and cadmium iodide. Single crystal X-ray diffraction analysis revealed that the Cd-MOF forms a one-dimensional (1D) polymeric structure and is finally adapted into a three-dimensional (3D) supramolecular network through various C–H---π interactions. The 3D framework features channels with cross-sectional dimensions of 17.31 × 20.31 Å2, aligned along the crystallographic b-axis, and accommodates coordinated water molecules. Remarkably, the Cd-MOF exhibits high fluorescence stability in aqueous solutions and is capable of selectively detecting 4-nitrophenol (4-NP) and 4-nitrotoluene (4-NT). The detection is characterized by high quenching constants and low detection limits, specifically 3.09 × 104 M−1 and 0.166 μM for 4-NP, and 3.09 × 104 M−1 and 0.184 μM for 4-NT. We argued that the fluorescence quenching of Cd-MOF in the presence of NACs is driven by competitive absorption and a synergistic interaction between the amidic functionalities and hinged ‘S’ atom in the ligand framework of Cd-MOF and NACs. This powerful synergy enables quick detection of NACs through triggered fluorescence quenching response.

Abstract Image

硫铰链l形配体基Cd(ii) -有机框架:一种针对环境硝基芳烃的荧光工具†
我们提出了镉基金属有机骨架(Cd- mof)的合成和详细的结构表征,其分子式为[Cd(L4-Py)(nipa)(H2O)]n,其中L4-Py代表n, n ' -(噻吩(4,1-苯基))二异烟碱酰胺,阴离子nipa2 -代表5-硝基间苯二甲酸盐。该Cd-MOF作为一种具有高选择性识别硝基芳香族化合物(NACs)的荧光探针已被研究。采用L4-Py配体、H2nipa共配体和碘化镉合成Cd-MOF。单晶x射线衍射分析表明,Cd-MOF形成一维(1D)聚合物结构,并通过各种C-H—π相互作用最终适应为三维(3D)超分子网络。三维框架的通道横截面尺寸为17.31 × 20.31 Å2,沿晶体学b轴排列,并容纳协调的水分子。值得注意的是,Cd-MOF在水溶液中表现出很高的荧光稳定性,能够选择性地检测4-硝基苯酚(4-NP)和4-硝基甲苯(4-NT)。该检测具有高猝灭常数和低检出限的特点,4-NP为3.09 × 104 M−1和0.166 μM, 4-NT为3.09 × 104 M−1和0.184 μM。我们认为,在NACs存在下,Cd-MOF的荧光猝灭是由Cd-MOF和NACs配体框架中的酰胺官能团和铰链‘ S ’原子之间的竞争吸收和协同相互作用驱动的。这种强大的协同作用可以通过触发荧光猝灭响应来快速检测NACs。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
CrystEngComm
CrystEngComm 化学-化学综合
CiteScore
5.50
自引率
9.70%
发文量
747
审稿时长
1.7 months
期刊介绍: Design and understanding of solid-state and crystalline materials
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