Structural Design of Zinc-Directed Heterometallic Uranyl Organic Frameworks: Multifunction Detection of Cr 2 O 7 2– and Metamitron Contaminants from Water

作者：Wensu Yang, Pei Lv, Jiayi Li, Xiaoping Jin, Ke Yang, Huan Dai, Wei Xu · 发表于：Crystal Growth & Design · 年份：2024 · DOI：10.1021/acs.cgd.4c01153 · 被引用次数：9 · 研究领域：Radioactive element chemistry and processing、Metal-Organic Frameworks: Synthesis and Applications、Covalent Organic Framework Applications

Based on the hard and soft acid and base (HSAB) theory, three heterometallic uranyl organic frameworks (UOFs), namely, [Zn(UO 2 )(npa) 2 (2,2′-bpy)(H 2 O)] ( 1 ), [Zn(UO 2 )(nip) 2 (2,9-dm-1,10-phen)] ( 2 ), and [Zn(UO 2 )(ntp) 2 (4,7-dm-1,10-phen)(H 2 O)]·(H 2 O) ( 3 ), have been solvothermally synthesized by using a variety of different substituted nitro-benzenedicarboxylic acid (H 2 npa = 3-nitrophthalic acid, H 2 nip = 5-nitroisophthalic acid, H 2 ntp = 2-nitroterephthalic acid) and uranyl zinc acetate, in the presence of N-bearing coligands, including 2,2′-bipyridine (2,2′-bpy), 2,9-dimethyl-1,10-phenanthroline (2,9-dm- 1,10-phen), and 4,7-dimethyl-1,10-phenanthroline (4,7-dm-1,10-phen). The results of single-crystal X-ray diffraction analysis show that each of them presents a heterometallic interaction between the uranyl and Zn 2+ centers. UOFs 2 and 3 adopt three-dimensional (3D) frameworks with different architectures, while UOF 1 exhibits a one-dimensional (1D) chain assembly. Furthermore, 1 can be used as a bifunctional luminescent sensor for the detection of metamitron (MMT) and Cr 2 O 7 2– in aqueous solution with the limit of detection (LOD) for 4.06 × 10 –6 and 2.52 × 10 –6 M, respectively. The sensing mechanism was also investigated in detail through ultraviolet–visible (UV–vis) absorption spectroscopy, density functional theory calculations (DFT), and fluorescence lifetime analysis. This work provides valuable guidance for the facile and effective design and c...