The construction of pore-functionalized, charged metal–organic frameworks (MOFs) promises critical fluorosensing of harmful organo-aromatics, toxic pollutant adsorption, and luminescent-ink based anticounterfeiting applications. We report the strategic construction of a non-penetrated framework, CSMCRI-4 (CSMCRI = Central Salt & Marine Chemicals Research Institute), from an electron-rich tricarboxylate ligand and the lightest metal-ion, which possesses anionic [Li₂(COO)₄] secondary building units (SBUs) and unbound oxygen atom decorated porous channels. The activated MOF (4a) displays extremely selective and ultrafast luminescent sensing of the lethal 2,6-dichloro-4-nitroaniline (DCNA) pesticide and the nitrofurazone (NZF) antibiotic with notable quenching and low limits of detection. It is imperative to stress the outstanding reusability of the MOF toward multicyclic sensing of both the organo-toxins. The reversibility of the host–guest interplay between the framework and individual analytes instigates fluorescence “off–on–off” switching, which is demonstrated by handy paper-strip monitoring. Density functional theory (DFT) calculation portrays unprecedented reshuffling of the molecular orbital energy levels in the electron-rich MOF by each nitro-organic, and verifies the framework-analyte supramolecular interactions. The extra-framework cations and free oxygen-atom affixed pore surface benefits selective encapsulation and sensitization of Tb³⁺ ions, which sharply change the emission color to green. The blue emission of the pristine MOF and modulated light emission in the Tb³⁺-doped material are utilized as highly regenerable luminescent-inks for vivid acronym encryption. The framework further illustrates charge-exclusive reversible adsorption of the toxic, cationic methylene blue (MB⁺) dye through bi-phasic colorimetric variation. DFT calculation precisely delineates the replacement of the pore-occluded guest by MB⁺, and explicitly validates its pore-fitting induced size selectivity over other dyes.

中文翻译：

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超轻型MOF，可作为各种有机毒素的氟控监测器：通过Tb3 +敏化作用实现尺寸排他的染料洗涤和防伪应用

具有孔功能的带电金属有机骨架（MOF）的构造有望对有害的有机芳香族化合物，有毒污染物吸附以及基于发光油墨的防伪应用进行关键的氟传感。我们报告了由富电子的三羧酸盐配体和最轻的金属离子（具有阴离子[Li ₂（COO））组成的非渗透性框架CSMCRI-4（CSMCRI =中央盐和海洋化学研究所）的战略建设₄ ]二级建筑单元（SBU）和未结合的氧原子修饰的多孔通道。激活的MOF（4a）对致命的2,6-二氯-4-硝基苯胺（DCNA）农药和硝基呋喃酮（NZF）抗生素具有极高的选择性和超快的发光感测，具有显着的猝灭和低检测限。必须强调MOF对两种有机毒素的多环感应具有出色的可重用性。框架与单个分析物之间主客相互作用的可逆性促使荧光“关-开-关”切换，这通过便捷的纸条监控得以证明。密度泛函理论（DFT）计算描绘了每个硝基有机物对富电子MOF中的分子轨道能级进行前所未有的改组，并验证了构架与分析物的超分子相互作用。³⁺离子，可将发射颜色急剧变为绿色。原始MOF的蓝色发射和掺有Tb ^3+的材料中的调制光被用作高度可再生的发光油墨，用于生动的首字母缩写加密。该框架进一步说明了通过双相比色变化对有毒的阳离子亚甲基蓝（MB ⁺）染料的电荷排斥可逆吸附。DFT计算精确地描述了用MB ⁺取代被孔堵塞的客体，并明确验证了其孔拟合引起的对其他染料的尺寸选择性。