Thermally Stable Anilate-Based 3D CPs/MOFs

The synthesis and characterization of two novel redox-active MOFs/CPs based on 3d transition metal ions and 3,6-ditriazolyl-2,5-dihydroxybenzoquinone (trz<sub>2</sub>An) are reported herein. By combining trz<sub>2</sub>An with Ni<sup>II</sup> and Mn<sup>II&l...

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Main Authors: Fabio Manna, Noemi Monni, Mariangela Oggianu, Juan Modesto Clemente-Juan, Miguel Clemente-León, Maria Laura Mercuri
Format: Article
Language:English
Published: MDPI AG 2025-06-01
Series:Crystals
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Online Access:https://www.mdpi.com/2073-4352/15/6/570
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author Fabio Manna
Noemi Monni
Mariangela Oggianu
Juan Modesto Clemente-Juan
Miguel Clemente-León
Maria Laura Mercuri
author_facet Fabio Manna
Noemi Monni
Mariangela Oggianu
Juan Modesto Clemente-Juan
Miguel Clemente-León
Maria Laura Mercuri
author_sort Fabio Manna
collection DOAJ
description The synthesis and characterization of two novel redox-active MOFs/CPs based on 3d transition metal ions and 3,6-ditriazolyl-2,5-dihydroxybenzoquinone (trz<sub>2</sub>An) are reported herein. By combining trz<sub>2</sub>An with Ni<sup>II</sup> and Mn<sup>II</sup> ions via the hydrothermal method, two phases, formulated as [Ni<sub>2</sub>(trz<sub>2</sub>An)<sub>2</sub>]·2.5H<sub>2</sub>O (<b>1</b>) and [Mn(trz<sub>2</sub>An)(H<sub>2</sub>O)]·1.5H<sub>2</sub>O (<b>2</b>), are obtained. Both compounds crystallize as neutral polymeric 3D frameworks, where the metal ions are coordinated through the oxygen atoms of the anilate linkers forming either straight (<b>1</b>) or zig-zag (<b>2</b>) 1D chains. In particular, (<b>1</b>) is a MOF, where these chains are connected through the nitrogen atom at the 4 position of the triazolyl group, which completes the coordination sphere of each metal ion, affording a 3D structure containing a void volume of 28.7% and voids that can be useful for the sorption of small molecules. Interestingly, (<b>1</b>) and (<b>2</b>) show a redox behavior due to the presence of the anilate linker, being reduced electrochemically in the −0.7 to −0.9 V range due to the benzoquinone–semiquinone one-electron reduction and magnetic behavior dominated by antiferromagnetic interactions in the anilate 1D chains.
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spelling doaj-art-eec328aa3c6d43e6a46cbddda277544a2025-08-20T03:24:39ZengMDPI AGCrystals2073-43522025-06-0115657010.3390/cryst15060570Thermally Stable Anilate-Based 3D CPs/MOFsFabio Manna0Noemi Monni1Mariangela Oggianu2Juan Modesto Clemente-Juan3Miguel Clemente-León4Maria Laura Mercuri5Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, I-09042 Monserrato, ItalyDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, I-09042 Monserrato, ItalyDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, I-09042 Monserrato, ItalyInstituto de Ciencia Molecular (ICMol), Universitat de València, Catedrático José Beltrán 2, 46980 Paterna, SpainInstituto de Ciencia Molecular (ICMol), Universitat de València, Catedrático José Beltrán 2, 46980 Paterna, SpainDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, I-09042 Monserrato, ItalyThe synthesis and characterization of two novel redox-active MOFs/CPs based on 3d transition metal ions and 3,6-ditriazolyl-2,5-dihydroxybenzoquinone (trz<sub>2</sub>An) are reported herein. By combining trz<sub>2</sub>An with Ni<sup>II</sup> and Mn<sup>II</sup> ions via the hydrothermal method, two phases, formulated as [Ni<sub>2</sub>(trz<sub>2</sub>An)<sub>2</sub>]·2.5H<sub>2</sub>O (<b>1</b>) and [Mn(trz<sub>2</sub>An)(H<sub>2</sub>O)]·1.5H<sub>2</sub>O (<b>2</b>), are obtained. Both compounds crystallize as neutral polymeric 3D frameworks, where the metal ions are coordinated through the oxygen atoms of the anilate linkers forming either straight (<b>1</b>) or zig-zag (<b>2</b>) 1D chains. In particular, (<b>1</b>) is a MOF, where these chains are connected through the nitrogen atom at the 4 position of the triazolyl group, which completes the coordination sphere of each metal ion, affording a 3D structure containing a void volume of 28.7% and voids that can be useful for the sorption of small molecules. Interestingly, (<b>1</b>) and (<b>2</b>) show a redox behavior due to the presence of the anilate linker, being reduced electrochemically in the −0.7 to −0.9 V range due to the benzoquinone–semiquinone one-electron reduction and magnetic behavior dominated by antiferromagnetic interactions in the anilate 1D chains.https://www.mdpi.com/2073-4352/15/6/570Coordination Polymers (CPs)Metal Organic Frameworks (MOFs)anilateredox active
spellingShingle Fabio Manna
Noemi Monni
Mariangela Oggianu
Juan Modesto Clemente-Juan
Miguel Clemente-León
Maria Laura Mercuri
Thermally Stable Anilate-Based 3D CPs/MOFs
Crystals
Coordination Polymers (CPs)
Metal Organic Frameworks (MOFs)
anilate
redox active
title Thermally Stable Anilate-Based 3D CPs/MOFs
title_full Thermally Stable Anilate-Based 3D CPs/MOFs
title_fullStr Thermally Stable Anilate-Based 3D CPs/MOFs
title_full_unstemmed Thermally Stable Anilate-Based 3D CPs/MOFs
title_short Thermally Stable Anilate-Based 3D CPs/MOFs
title_sort thermally stable anilate based 3d cps mofs
topic Coordination Polymers (CPs)
Metal Organic Frameworks (MOFs)
anilate
redox active
url https://www.mdpi.com/2073-4352/15/6/570
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AT mariangelaoggianu thermallystableanilatebased3dcpsmofs
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AT miguelclementeleon thermallystableanilatebased3dcpsmofs
AT marialauramercuri thermallystableanilatebased3dcpsmofs