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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...

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Autores principales: Moroni, Marco, Nardo, Luca, Maspero, Angelo, Vesco, Guglielmo, Lamperti, Marco, Scapinello, Luca, Vismara, Rebecca, Navarro, Jorge A. R., Monticelli, Damiano, Penoni, Andrea, Mella, Massimo, Galli, Simona
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
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
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author Moroni, Marco
Nardo, Luca
Maspero, Angelo
Vesco, Guglielmo
Lamperti, Marco
Scapinello, Luca
Vismara, Rebecca
Navarro, Jorge A. R.
Monticelli, Damiano
Penoni, Andrea
Mella, Massimo
Galli, Simona
author_facet Moroni, Marco
Nardo, Luca
Maspero, Angelo
Vesco, Guglielmo
Lamperti, Marco
Scapinello, Luca
Vismara, Rebecca
Navarro, Jorge A. R.
Monticelli, Damiano
Penoni, Andrea
Mella, Massimo
Galli, Simona
author_sort Moroni, Marco
collection PubMed
description [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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spelling pubmed-101005372023-04-14 Mercury Clathration-Driven Phase Transition in a Luminescent Bipyrazolate Metal–Organic Framework: A Multitechnique Investigation Moroni, Marco Nardo, Luca Maspero, Angelo Vesco, Guglielmo Lamperti, Marco Scapinello, Luca Vismara, Rebecca Navarro, Jorge A. R. Monticelli, Damiano Penoni, Andrea Mella, Massimo Galli, Simona Chem Mater [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. American Chemical Society 2023-03-22 /pmc/articles/PMC10100537/ /pubmed/37063591 http://dx.doi.org/10.1021/acs.chemmater.2c03801 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Moroni, Marco
Nardo, Luca
Maspero, Angelo
Vesco, Guglielmo
Lamperti, Marco
Scapinello, Luca
Vismara, Rebecca
Navarro, Jorge A. R.
Monticelli, Damiano
Penoni, Andrea
Mella, Massimo
Galli, Simona
Mercury Clathration-Driven Phase Transition in a Luminescent Bipyrazolate Metal–Organic Framework: A Multitechnique Investigation
title Mercury Clathration-Driven Phase Transition in a Luminescent Bipyrazolate Metal–Organic Framework: A Multitechnique Investigation
title_full Mercury Clathration-Driven Phase Transition in a Luminescent Bipyrazolate Metal–Organic Framework: A Multitechnique Investigation
title_fullStr Mercury Clathration-Driven Phase Transition in a Luminescent Bipyrazolate Metal–Organic Framework: A Multitechnique Investigation
title_full_unstemmed Mercury Clathration-Driven Phase Transition in a Luminescent Bipyrazolate Metal–Organic Framework: A Multitechnique Investigation
title_short Mercury Clathration-Driven Phase Transition in a Luminescent Bipyrazolate Metal–Organic Framework: A Multitechnique Investigation
title_sort mercury clathration-driven phase transition in a luminescent bipyrazolate metal–organic framework: a multitechnique investigation
url 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
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