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Mercury Clathration-Driven Phase Transition in a Luminescent Bipyrazolate Metal–Organic Framework: A Multitechnique Investigation
[Image: see text] Mercury is one of the most toxic heavy metals. By virtue of its triple bond, the novel ligand 1,2-bis(1H-pyrazol-4-yl)ethyne (H(2)BPE) was expressly designed and synthesized to devise metal–organic frameworks (MOFs) exhibiting high chemical affinity for mercury. Two MOFs, Zn(BPE) a...
Autores principales: | , , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10100537/ https://www.ncbi.nlm.nih.gov/pubmed/37063591 http://dx.doi.org/10.1021/acs.chemmater.2c03801 |
Sumario: | [Image: see text] Mercury is one of the most toxic heavy metals. By virtue of its triple bond, the novel ligand 1,2-bis(1H-pyrazol-4-yl)ethyne (H(2)BPE) was expressly designed and synthesized to devise metal–organic frameworks (MOFs) exhibiting high chemical affinity for mercury. Two MOFs, Zn(BPE) and Zn(BPE)·nDMF [interpenetrated i-Zn and noninterpenetrated ni-Zn·S, respectively; DMF = dimethylformamide], were isolated as microcrystalline powders. While i-Zn is stable in water for at least 15 days, its suspension in HgCl(2) aqueous solutions prompts its conversion into HgCl(2)@ni-Zn. A multitechnique approach allowed us to shed light onto the observed HgCl(2)-triggered i-Zn-to-HgCl(2)@ni-Zn transformation at the molecular level. Density functional theory calculations on model systems suggested that HgCl(2) interacts via the mercury atom with the carbon–carbon triple bond exclusively in ni-Zn. Powder X-ray diffraction enabled us to quantify the extent of the i-Zn-to-HgCl(2)@ni-Zn transition in 100–5000 ppm HgCl(2 (aq)) solutions, while X-ray fluorescence and inductively coupled plasma-mass spectrometry allowed us to demonstrate that HgCl(2) is quantitatively sequestered from the aqueous phase. Irradiating at 365 nm, an intense fluorescence is observed at 470 nm for ni-Zn·S, which is partially quenched for i-Zn. This spectral benchmark was exploited to monitor in real time the i-Zn-to-HgCl(2)@ni-Zn conversion kinetics at different HgCl(2 (aq)) concentrations. A sizeable fluorescence increase was observed, within a 1 h time lapse, even at a concentration of 5 ppb. Overall, this comprehensive investigation unraveled an intriguing molecular mechanism, featuring the disaggregation of a water-stable MOF in the presence of HgCl(2) and the self-assembly of a different crystalline phase around the pollutant, which is sequestered and simultaneously quantified by means of a luminescence change. Such a case study might open the way to new-conception strategies to achieve real-time sensing of mercury-containing pollutants in wastewaters and, eventually, pursue their straightforward and cost-effective purification. |
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