Metallic–Organic Cages (MOCs) with Heterometallic Character: Flexibility-Enhancing MOFs
The dichotomy between metal–organic frameworks (MOFs) and metal–organic cages (MOCs) opens up the research spectrum of two fields which, despite having similarities, both have their advantages and disadvantages. Due to the fact that they have cavities inside, they also have applicability in the poro...
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MDPI AG
2023-02-01
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| Series: | Catalysts |
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| Online Access: | https://www.mdpi.com/2073-4344/13/2/317 |
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| author | Sergio Posada-Pérez Jordi Poater Naeimeh Bahri-Laleh Albert Poater |
| author_facet | Sergio Posada-Pérez Jordi Poater Naeimeh Bahri-Laleh Albert Poater |
| author_sort | Sergio Posada-Pérez |
| collection | DOAJ |
| description | The dichotomy between metal–organic frameworks (MOFs) and metal–organic cages (MOCs) opens up the research spectrum of two fields which, despite having similarities, both have their advantages and disadvantages. Due to the fact that they have cavities inside, they also have applicability in the porosity sector. Bloch and coworkers within this evolution from MOFs to MOCs manage to describe a MOC with a structure of Cu<sub>2</sub> paddlewheel Cu<sub>4</sub>L<sub>4</sub> (L = bis(pyrazolyl)methane) with high precision thanks to crystallographic analyses of X-ray diffraction and also SEM-EDX. Then, also at the same level of concreteness, they were able to find the self-assembly of Pd(II)Cl<sub>2</sub> moieties on the available nitrogen donor atoms leading to a [Cu<sub>4</sub>(L(PdCl<sub>2</sub>))<sub>4</sub>] structure. Here, calculations of the DFT density functional allow us to reach an unusual precision given the magnitude and structural complexity, explaining how a pyrazole ring of each bis(pyprazolyl)methane ligand must rotate from an <i>anti</i> to a <i>syn</i> conformation, and a truncation of the MOC structure allows us to elucidate, in the absence of the MOC constraint and its packing in the crystal, that the rotation is almost barrierless, as well as also explain the relative stability of the different conformations, with the <i>anti</i> being the most stable conformation. Characterization calculations with Mayer bond orders (MBO) and noncovalent interaction (NCI) plots discern what is important in the interaction of this type of cage with PdCl<sub>2</sub> moieties, also CuCl<sub>2</sub> by analogy, as well as simple molecules of water, since the complex is stable in this solvent. However, the L ligand is proved to not have the ability to stabilize an H<sub>2</sub>O molecule. |
| first_indexed | 2024-03-11T09:02:04Z |
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| institution | Directory Open Access Journal |
| issn | 2073-4344 |
| language | English |
| last_indexed | 2024-03-11T09:02:04Z |
| publishDate | 2023-02-01 |
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| spelling | doaj.art-81e9f347d27a4d68912f5d2ef4cdaeef2023-11-16T19:41:26ZengMDPI AGCatalysts2073-43442023-02-0113231710.3390/catal13020317Metallic–Organic Cages (MOCs) with Heterometallic Character: Flexibility-Enhancing MOFsSergio Posada-Pérez0Jordi Poater1Naeimeh Bahri-Laleh2Albert Poater3Institut de Química Computacional i Catàlisi, Departament de Química, Universitat de Girona, c/M<sup>a</sup> Aurèlia Capmany, 17003 Girona, SpainDepartament de Química Inorgànica i Orgànica & IQTCUB, Universitat de Barcelona, 08028 Barcelona, SpainPolymerization Engineering Department, Iran Polymer and Petrochemical Institute (IPPI), Tehran P.O. Box 14965/115, IranInstitut de Química Computacional i Catàlisi, Departament de Química, Universitat de Girona, c/M<sup>a</sup> Aurèlia Capmany, 17003 Girona, SpainThe dichotomy between metal–organic frameworks (MOFs) and metal–organic cages (MOCs) opens up the research spectrum of two fields which, despite having similarities, both have their advantages and disadvantages. Due to the fact that they have cavities inside, they also have applicability in the porosity sector. Bloch and coworkers within this evolution from MOFs to MOCs manage to describe a MOC with a structure of Cu<sub>2</sub> paddlewheel Cu<sub>4</sub>L<sub>4</sub> (L = bis(pyrazolyl)methane) with high precision thanks to crystallographic analyses of X-ray diffraction and also SEM-EDX. Then, also at the same level of concreteness, they were able to find the self-assembly of Pd(II)Cl<sub>2</sub> moieties on the available nitrogen donor atoms leading to a [Cu<sub>4</sub>(L(PdCl<sub>2</sub>))<sub>4</sub>] structure. Here, calculations of the DFT density functional allow us to reach an unusual precision given the magnitude and structural complexity, explaining how a pyrazole ring of each bis(pyprazolyl)methane ligand must rotate from an <i>anti</i> to a <i>syn</i> conformation, and a truncation of the MOC structure allows us to elucidate, in the absence of the MOC constraint and its packing in the crystal, that the rotation is almost barrierless, as well as also explain the relative stability of the different conformations, with the <i>anti</i> being the most stable conformation. Characterization calculations with Mayer bond orders (MBO) and noncovalent interaction (NCI) plots discern what is important in the interaction of this type of cage with PdCl<sub>2</sub> moieties, also CuCl<sub>2</sub> by analogy, as well as simple molecules of water, since the complex is stable in this solvent. However, the L ligand is proved to not have the ability to stabilize an H<sub>2</sub>O molecule.https://www.mdpi.com/2073-4344/13/2/317COFMOFmetallic–organic cagepyrazolebis(pyrazolyl)methaneheterometallic |
| spellingShingle | Sergio Posada-Pérez Jordi Poater Naeimeh Bahri-Laleh Albert Poater Metallic–Organic Cages (MOCs) with Heterometallic Character: Flexibility-Enhancing MOFs Catalysts COF MOF metallic–organic cage pyrazole bis(pyrazolyl)methane heterometallic |
| title | Metallic–Organic Cages (MOCs) with Heterometallic Character: Flexibility-Enhancing MOFs |
| title_full | Metallic–Organic Cages (MOCs) with Heterometallic Character: Flexibility-Enhancing MOFs |
| title_fullStr | Metallic–Organic Cages (MOCs) with Heterometallic Character: Flexibility-Enhancing MOFs |
| title_full_unstemmed | Metallic–Organic Cages (MOCs) with Heterometallic Character: Flexibility-Enhancing MOFs |
| title_short | Metallic–Organic Cages (MOCs) with Heterometallic Character: Flexibility-Enhancing MOFs |
| title_sort | metallic organic cages mocs with heterometallic character flexibility enhancing mofs |
| topic | COF MOF metallic–organic cage pyrazole bis(pyrazolyl)methane heterometallic |
| url | https://www.mdpi.com/2073-4344/13/2/317 |
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