Metal-Organic Framework vs. Coordination Polymer—Influence of the Lanthanide on the Nature of the Heteroleptic Anilate/Terephtalate 3D Network
Metal-organic frameworks (MOFs), whose definition has been regularly debated, are a sub-class of coordination polymers (CPs) which may feature both an overall 3D architecture and some degree of porosity. In this context, MOFs based on lanthanides (Ln-MOFs) could find many applications due to the com...
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| Format: | Article |
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MDPI AG
2022-05-01
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| Series: | Crystals |
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| Online Access: | https://www.mdpi.com/2073-4352/12/6/763 |
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| author | Mariangela Oggianu Fabio Manna Suchithra Ashoka Sahadevan Narcis Avarvari Alexandre Abhervé Maria Laura Mercuri |
| author_facet | Mariangela Oggianu Fabio Manna Suchithra Ashoka Sahadevan Narcis Avarvari Alexandre Abhervé Maria Laura Mercuri |
| author_sort | Mariangela Oggianu |
| collection | DOAJ |
| description | Metal-organic frameworks (MOFs), whose definition has been regularly debated, are a sub-class of coordination polymers (CPs) which may feature both an overall 3D architecture and some degree of porosity. In this context, MOFs based on lanthanides (Ln-MOFs) could find many applications due to the combination of sorption properties and magnetic/luminescent behaviors. Here we report rare examples of 3D Ln-CPs based on anilate linkers, obtained under solvothermal conditions using a heteroleptic strategy. The three compounds of formula [Yb<sub>2</sub>(μ-ClCNAn)<sub>2</sub>(μ-F<sub>4</sub>BDC)(H<sub>2</sub>O)<sub>4</sub>]·(H<sub>2</sub>O)<sub>3</sub> (<b>1</b>), [Er<sub>2</sub>(μ-ClCNAn)<sub>2</sub>(μ-F<sub>4</sub>BDC)(H<sub>2</sub>O)<sub>4</sub>]·(H<sub>2</sub>O)<sub>4</sub> (<b>2</b>) and [Eu<sub>2</sub>(μ-ClCNAn)<sub>2</sub>(μ-F<sub>4</sub>BDC)(H<sub>2</sub>O)<sub>6</sub>] (<b>3</b>) have been characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and optical measurements. Structural characterization revealed that compounds <b>1</b> and <b>2</b> present an interesting MOF architecture with extended rectangular cavities which are only filled with water molecules. On the other hand, compound <b>3</b> shows a much more complex topology with no apparent cavities. We discuss here the origins of such differences and highlight the crucial role of the Ln(III) ion nature for the topology of the CP. Compounds <b>1</b> and <b>2</b> now offer a playground to investigate the possible synergy between gas/solvent sorption and magnetic/luminescent properties of Ln-MOFs. |
| first_indexed | 2024-03-10T00:04:31Z |
| format | Article |
| id | doaj.art-a03ea32524d54c72afd273e91debfe64 |
| institution | Directory Open Access Journal |
| issn | 2073-4352 |
| language | English |
| last_indexed | 2024-03-10T00:04:31Z |
| publishDate | 2022-05-01 |
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| series | Crystals |
| spelling | doaj.art-a03ea32524d54c72afd273e91debfe642023-11-23T16:11:26ZengMDPI AGCrystals2073-43522022-05-0112676310.3390/cryst12060763Metal-Organic Framework vs. Coordination Polymer—Influence of the Lanthanide on the Nature of the Heteroleptic Anilate/Terephtalate 3D NetworkMariangela Oggianu0Fabio Manna1Suchithra Ashoka Sahadevan2Narcis Avarvari3Alexandre Abhervé4Maria Laura Mercuri5Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, I-09042 Monserrato, Cagliari, ItalyDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, I-09042 Monserrato, Cagliari, ItalyDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, I-09042 Monserrato, Cagliari, ItalyUniv Angers, CNRS, MOLTECH-Anjou, SFR MATRIX, F-49000 Angers, FranceUniv Angers, CNRS, MOLTECH-Anjou, SFR MATRIX, F-49000 Angers, FranceDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, I-09042 Monserrato, Cagliari, ItalyMetal-organic frameworks (MOFs), whose definition has been regularly debated, are a sub-class of coordination polymers (CPs) which may feature both an overall 3D architecture and some degree of porosity. In this context, MOFs based on lanthanides (Ln-MOFs) could find many applications due to the combination of sorption properties and magnetic/luminescent behaviors. Here we report rare examples of 3D Ln-CPs based on anilate linkers, obtained under solvothermal conditions using a heteroleptic strategy. The three compounds of formula [Yb<sub>2</sub>(μ-ClCNAn)<sub>2</sub>(μ-F<sub>4</sub>BDC)(H<sub>2</sub>O)<sub>4</sub>]·(H<sub>2</sub>O)<sub>3</sub> (<b>1</b>), [Er<sub>2</sub>(μ-ClCNAn)<sub>2</sub>(μ-F<sub>4</sub>BDC)(H<sub>2</sub>O)<sub>4</sub>]·(H<sub>2</sub>O)<sub>4</sub> (<b>2</b>) and [Eu<sub>2</sub>(μ-ClCNAn)<sub>2</sub>(μ-F<sub>4</sub>BDC)(H<sub>2</sub>O)<sub>6</sub>] (<b>3</b>) have been characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and optical measurements. Structural characterization revealed that compounds <b>1</b> and <b>2</b> present an interesting MOF architecture with extended rectangular cavities which are only filled with water molecules. On the other hand, compound <b>3</b> shows a much more complex topology with no apparent cavities. We discuss here the origins of such differences and highlight the crucial role of the Ln(III) ion nature for the topology of the CP. Compounds <b>1</b> and <b>2</b> now offer a playground to investigate the possible synergy between gas/solvent sorption and magnetic/luminescent properties of Ln-MOFs.https://www.mdpi.com/2073-4352/12/6/763metal-organic frameworklanthanideschlorocyananilatetetrafluoroterephtalate |
| spellingShingle | Mariangela Oggianu Fabio Manna Suchithra Ashoka Sahadevan Narcis Avarvari Alexandre Abhervé Maria Laura Mercuri Metal-Organic Framework vs. Coordination Polymer—Influence of the Lanthanide on the Nature of the Heteroleptic Anilate/Terephtalate 3D Network Crystals metal-organic framework lanthanides chlorocyananilate tetrafluoroterephtalate |
| title | Metal-Organic Framework vs. Coordination Polymer—Influence of the Lanthanide on the Nature of the Heteroleptic Anilate/Terephtalate 3D Network |
| title_full | Metal-Organic Framework vs. Coordination Polymer—Influence of the Lanthanide on the Nature of the Heteroleptic Anilate/Terephtalate 3D Network |
| title_fullStr | Metal-Organic Framework vs. Coordination Polymer—Influence of the Lanthanide on the Nature of the Heteroleptic Anilate/Terephtalate 3D Network |
| title_full_unstemmed | Metal-Organic Framework vs. Coordination Polymer—Influence of the Lanthanide on the Nature of the Heteroleptic Anilate/Terephtalate 3D Network |
| title_short | Metal-Organic Framework vs. Coordination Polymer—Influence of the Lanthanide on the Nature of the Heteroleptic Anilate/Terephtalate 3D Network |
| title_sort | metal organic framework vs coordination polymer influence of the lanthanide on the nature of the heteroleptic anilate terephtalate 3d network |
| topic | metal-organic framework lanthanides chlorocyananilate tetrafluoroterephtalate |
| url | https://www.mdpi.com/2073-4352/12/6/763 |
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