Mechanistic Insights into Solvent-Mediated Halide-Specific Irreversible Transformation of Cu-MOF with Iodide Detection Capability

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F25%3A10497839" target="_blank" >RIV/00216208:11310/25:10497839 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=DqQvlav-k-" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=DqQvlav-k-</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.inorgchem.4c04816" target="_blank" >10.1021/acs.inorgchem.4c04816</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Mechanistic Insights into Solvent-Mediated Halide-Specific Irreversible Transformation of Cu-MOF with Iodide Detection Capability

Popis výsledku v původním jazyce

The fascinating feature of metal-organic frameworks is that they can respond to external stimuli, unlike other inorganic materials. This feature corresponds to the framework&apos;s flexibility, which originates with the long-range crystalline order of the framework accompanied by cooperative structural transformability. We have synthesized a novel metal-organic framework comprised of Cu(I) nodes with pyrazine linkers and benzene-1,3,5-tricarboxylate acting as template anions, named CUCAM-1 [Cu(Py)2(BTC)](n). In the presence of polar solvent systems, CUCAM-1 undergoes an irreversible structural transformation to yield a mixed phase that consists of HKUST-1 [Cu(3)(BTC)2(H2O)(3)](n) and another CUCAM-2 [Cu(Py)(BTC)](n) MOFs, whose novel structure is successfully revealed by continuous rotation electron diffraction from the mixture. In this structural transformation, a new ligand exchange occurs where template anions become ligands, confirmed by single crystal X-ray analysis. Further, structural transformation and the mechanism are explained by ab initio molecular dynamics (AIMD) simulations. Interestingly, different halides (F(-), Cl(-), and Br(-)) can be accompanied to affect/control the composition of the second phase by favoring the formation of the HKUST-1 phase over CUCAM-2, which was evident by the powder X-ray diffraction studies. Furthermore, the structural transformation induced by I(-) resulted in a colorimetric response due to the formation of a new MOF CUCAM-3, paving the way for use as an iodide detector.

Název v anglickém jazyce

Mechanistic Insights into Solvent-Mediated Halide-Specific Irreversible Transformation of Cu-MOF with Iodide Detection Capability

Popis výsledku anglicky

The fascinating feature of metal-organic frameworks is that they can respond to external stimuli, unlike other inorganic materials. This feature corresponds to the framework&apos;s flexibility, which originates with the long-range crystalline order of the framework accompanied by cooperative structural transformability. We have synthesized a novel metal-organic framework comprised of Cu(I) nodes with pyrazine linkers and benzene-1,3,5-tricarboxylate acting as template anions, named CUCAM-1 [Cu(Py)2(BTC)](n). In the presence of polar solvent systems, CUCAM-1 undergoes an irreversible structural transformation to yield a mixed phase that consists of HKUST-1 [Cu(3)(BTC)2(H2O)(3)](n) and another CUCAM-2 [Cu(Py)(BTC)](n) MOFs, whose novel structure is successfully revealed by continuous rotation electron diffraction from the mixture. In this structural transformation, a new ligand exchange occurs where template anions become ligands, confirmed by single crystal X-ray analysis. Further, structural transformation and the mechanism are explained by ab initio molecular dynamics (AIMD) simulations. Interestingly, different halides (F(-), Cl(-), and Br(-)) can be accompanied to affect/control the composition of the second phase by favoring the formation of the HKUST-1 phase over CUCAM-2, which was evident by the powder X-ray diffraction studies. Furthermore, the structural transformation induced by I(-) resulted in a colorimetric response due to the formation of a new MOF CUCAM-3, paving the way for use as an iodide detector.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

1520-510X

Svazek periodika

64

Číslo periodika v rámci svazku

7

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

9

Strana od-do

3326-3334

Kód UT WoS článku

001420626000001

EID výsledku v databázi Scopus

2-s2.0-85217801257