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Inorganics
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Metal-Organic Frameworks: A Diverse Class of Compounds with Structures and...
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Metal-Organic Frameworks: A Diverse Class of Compounds with Structures and Applications Only Limited by the Imagination of the Researcher

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: closed (28 February 2022) | Viewed by 14182

Special Issue Editors

Prof. Dr. Lars Öhrström

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Guest Editor
Department of Chemistry and Chemical Engineering, Division of Chemistry and Biochemistry, Chalmers University of Technology, SE-412 96 Gothenburg, Sweden
Interests: metal-organic frameworks
Prof. Dr. Susan Bourne

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Guest Editor
Centre for Supramolecular Chemistry Research, Department of Chemistry, University of Cape Town, Rondebosch 7701, South Africa
Interests: supramolecular chemistry
Dr. Francoise M. Amombo Noa

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Guest Editor
Department of Chemistry and Chemical Engineering, Chalmers University of Technology, SE 41296 Gothenburg, Sweden
Interests: supramolecular chemistry (halogen bond, co-crystal, pharmaceutical co-crystal, crystal growth); reticular chemistry (metal-organic frameworks, covalent-organic frameworks); crystallography

Special Issue Information

Dear Colleagues,

This Special Issue focuses on the design, synthesis, and study of metal–organic frameworks (MOFs), a diverse class of materials which usually form aesthetic and extremely beautiful extended coordination networks with an organic ligand and a metal ion or metal cluster in 1-dimensional, 2-dimensional, and 3-dimensional frameworks. MOF chemistry has tremendously advanced with various applications, such as gas storage, drug delivery materials, heterogenous catalysts, water harvesting, and many more. The assembly and structure-directing role of the multimetallic secondary building unit (SBU) is central to the synthesis and understanding of MOFs, which is why some crystal structures of these stunning extended molecular architectures also illustrate fascinating magnetic and electronic properties. There is also more of an interplay of theoretical and experimental approaches, further increasing the scope of MOF research. The goal of this Special Issue is to assemble contributions from scientists with similar research interests and let their imagination be the limit of their discoveries. We invite original contributions as well as short, focused reviews.

Prof. Dr. Lars Öhrström
Prof. Dr. Susan Bourne
Dr. Francoise M. Amombo Noa
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Inorganics is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Metal–organic frameworks
  • Coordination network
  • Secondary building unit
  • Magnetism
  • Electronic properties
  • Topology
  • Thermo- and solvatochromic properties
  • Catalysis
  • Redox-active materials
  • Synthesis

Published Papers (5 papers)

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Research

17 pages, 3475 KiB  
Article
Synthesis and Crystal Structures of Mn(II) and Co(II) Complexes as Catalysts for Oxidation of Cyclohexanone
by Adedibu C. Tella, Aaron Y. Isaac, Hadley S. Clayton, Adeniyi S. Ogunlaja, Aswathy T. Venugopalan, Marimuthu Prabu and Raja Thirumalaiswamy
Inorganics 2022, 10(7), 100; https://doi.org/10.3390/inorganics10070100 - 10 Jul 2022
Cited by 3 | Viewed by 1688
Abstract
The global demand on adipic usage in the production of plasticizers and synthetic polyamide is increasing. In line with the search for an efficient and energy-conserving way to isolate adipic acid (AA) in good yields, this paper introduces the oxidization of cyclohexanone utilizing [...] Read more.
The global demand on adipic usage in the production of plasticizers and synthetic polyamide is increasing. In line with the search for an efficient and energy-conserving way to isolate adipic acid (AA) in good yields, this paper introduces the oxidization of cyclohexanone utilizing two new coordination compounds, [Mn(2,6-pydc)2](imi) (1) and [Co(H2pza)2(H2O)2(NO3)].NO3 (2), as catalysts. Compounds 1 and 2 were synthesized by room temperature and refluxing methods, and characterized by spectral analyses (IR and UV-Vis.), SEM, BET, TGA, elemental, and X-ray crystallography. The single crystal structure of compound 1 revealed that pyridinedicarboxylate (2,6-pydc) and imidazole (imi) moieties were coordinated to the Mn(II) atom through imine nitrogen and deprotonated oxygen atoms, to form an undistorted octahedral coordination geometry with the N2O4 donor set. The axial and equatorial planes containing O2, O4, O5, and O7 atoms were from two adjacent 2,6-pydc ligands which formed the unidendate donor ligand; imi, on the other hand, acted as a bidendate donor ligand. For compound 2, the Co(II) atom was being coordinated by two pyrazinamide (H2pza) moieties, which acted as an unidendate donor ligand; two water molecules occupying the axial position, and one nitrate molecule occupying the apical position, were within the coordination sphere; a nitrate molecule was disordered outside the coordination sphere. The distance, 4.658 Å, between the Co1 atom and the N8 atom of the uncoordinated nitrate molecule, was within the range reported elsewhere. Cyclohexanone peroxidation experiments revealed that compound 1 exhibited unique catalytic performance by giving a 72.8% yield in adipic acid, in comparison to the 71.3% yield obtained with compound 2. The yields in AA were maintained by way of recyclability evaluation. The reaction kinetics of compound 2 gave less activation energy, Ea 2938 J mol−1, while the thermodynamic parameters indicated that the chemical reactivity of cyclohexanone on the active surfaces of compounds 1 and 2 was via monolayer physisorption. Full article
(This article belongs to the Special Issue Metal-Organic Frameworks: A Diverse Class of Compounds with Structures and Applications Only Limited by the Imagination of the Researcher)
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16 pages, 3762 KiB  
Article
Supramolecular Frameworks and a Luminescent Coordination Polymer from New β-Diketone/Tetrazole Ligands
by Delia Blasi, Pierluigi Mercandelli and Lucia Carlucci
Inorganics 2022, 10(4), 55; https://doi.org/10.3390/inorganics10040055 - 18 Apr 2022
Cited by 2 | Viewed by 1897
Abstract
Mixed multidentate linkers with donor groups of different types can be fruitfully exploited in the self-assembly of coordination polymers (CPs) and Metal-Organic Frameworks (MOFs). In this work we develop new ligands containing a β-diketone chelating functionality, to better control the stereochemistry at the [...] Read more.
Mixed multidentate linkers with donor groups of different types can be fruitfully exploited in the self-assembly of coordination polymers (CPs) and Metal-Organic Frameworks (MOFs). In this work we develop new ligands containing a β-diketone chelating functionality, to better control the stereochemistry at the metal center, and tetrazolyl multidentate bridging groups, a combination not yet explored for networking with metal ions. The new ligands, 1,3-bis(4-(1H-tetrazol-5-yl)phenyl)-1,3-propanedione (H3L1) and 1-phenyl-3-(4-(1H-tetrazol-5-yl)phenyl)-1,3-propanedione (H2L2), are synthesized from the corresponding nitrile precursors by [2+3] dipolar cycloaddition of azide under metal-free catalytic conditions. Crystal structure analysis evidences the involvement of tetrazolyl fragments in multiple hydrogen bonding giving 2D and 1D supramolecular frameworks. Reactivity of the new ligands with different metal salts indicates good coordinating ability, and we report the preparation and structural characterization of the tris–chelate complex [Fe(HL1)3]3− (1) and the homometallic 2D CP [ZnL2(DMSO)] (2). In compound 1 only the diketonate donor is used, whereas the partially deprotonated tetrazolyl groups are involved in hydrogen bonding, giving rise to a 2D supramolecular framework of (6,3)IIa topological type. In compound 2 the ligand is completely deprotonated and uses both the diketonate donor (chelating) and the tetrazolate fragment (bridging) to coordinate the Zn(II) ions. The resulting neutral 2D network of sql topology shows luminescence in the solid state, which is red shifted with respect to the free ligand. Interestingly, it can be easily exfoliated in water to give a luminescent colloidal solution. Full article
(This article belongs to the Special Issue Metal-Organic Frameworks: A Diverse Class of Compounds with Structures and Applications Only Limited by the Imagination of the Researcher)
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13 pages, 3303 KiB  
Article
Hydrogenation of Carbon Dioxide to Formate Using a Cadmium-Based Metal–Organic Framework Impregnated with Nanoparticles
by Nyasha Makuve, James Darkwa, Gift Mehlana and Banothile C. E. Makhubela
Inorganics 2022, 10(3), 30; https://doi.org/10.3390/inorganics10030030 - 25 Feb 2022
Cited by 6 | Viewed by 2596
Abstract
The burning of fossil fuels to meet energy demands has increased carbon dioxide (CO2) in the atmosphere, causing global warming and associated climate change. Therefore, new materials are being developed to capture CO2 effectively, limit its impact on the environment, [...] Read more.
The burning of fossil fuels to meet energy demands has increased carbon dioxide (CO2) in the atmosphere, causing global warming and associated climate change. Therefore, new materials are being developed to capture CO2 effectively, limit its impact on the environment, and store and/or utilise it as an abundant C1 building block. In this study, we investigate a cadmium(II) metal–organic framework, [Cd(bdc)(DMF)]n (MOF1), synthesised by treating benzene-1,4-dicarboxylic acid with four equivalents of [Cd(NO3)2]. MOF1 was then used to support Pd, Ni, and Pt nanoparticles in forming MOF1/Pd MOF1/Ni and MOF1/Pt, respectively. These MOF-based materials were characterised using powder X-ray diffraction (PXRD), Fourier-transform infrared (FTIR), energy-dispersive X-ray spectroscopy (EDX), selected area electron diffraction (SAED), and high-resolution transmission electron microscopy (HR-TEM). MOF1/Pd MOF1/Ni and MOF1/Pt proved highly active in the catalytic hydrogenation of CO2 to formate selectively; in contrast, MOF1 did not hydrogenate CO2 to formate. The MOF1/Pd, MOF1/Ni, and MOF1/Pt catalysts produced formate selectively, with the highest TON of 1500 (TOF of 69 h−1) achieved using MOF1/Pd as the catalyst at 170 °C within 2 h. A formate yield of 98% was obtained, which demonstrates that the combination of nanoparticles and MOFs greatly enhances the catalytic activity of the active sites. Full article
(This article belongs to the Special Issue Metal-Organic Frameworks: A Diverse Class of Compounds with Structures and Applications Only Limited by the Imagination of the Researcher)
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8 pages, 13242 KiB  
Article
Hybrid Metal-Organic Framework-Cellulose Materials Retaining High Porosity: ZIF-8@Cellulose Nanofibrils
by Johannes Thunberg, Savannah C. Zacharias, Merima Hasani, Olayinka. A. Oyetunji, Francoise M. Amombo Noa, Gunnar Westman and Lars Öhrström
Inorganics 2021, 9(11), 84; https://doi.org/10.3390/inorganics9110084 - 20 Nov 2021
Cited by 9 | Viewed by 3409
Abstract
Metal-organic frameworks have attracted a great deal of attention for future applications in numerous areas, including gas adsorption. However, in order for them to reach their full potential a substrate to provide an anchor may be needed. Ideally, this substrate should be environmentally [...] Read more.
Metal-organic frameworks have attracted a great deal of attention for future applications in numerous areas, including gas adsorption. However, in order for them to reach their full potential a substrate to provide an anchor may be needed. Ideally, this substrate should be environmentally friendly and renewable. Cellulose nanofibrils show potential in this area. Here we present a hybrid material created from the self-assembly of zeolitic imidazolate framework (ZIF-8) nanocrystals on cellulose nanofibrils (CNF) in aqueous medium. The CNF/ZIF-8 was freeze dried and formed free standing materials suitable for gas adsorption. A BET area of 1014 m2 g−1 was achieved for the CNF/ZIF-8 hybrid materials ZIF-8@cellulose which is comparable with reported values for free standing ZIF-8 materials, 1600 m2 g−1, considering the dilution with cellulose, and a considerable enhancement compared to CNF on its own, 32 m2 g−1. Full article
(This article belongs to the Special Issue Metal-Organic Frameworks: A Diverse Class of Compounds with Structures and Applications Only Limited by the Imagination of the Researcher)
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13 pages, 4300 KiB  
Article
Nanostructure and Luminescent Properties of Bimetallic Lanthanide Eu/Gd, Tb/Gd and Eu/Tb Coordination Polymers
by Helena Brunckova, Erika Mudra, Lucas Rocha, Eduardo Nassar, Willian Nascimento, Hristo Kolev, Maksym Lisnichuk, Alexandra Kovalcikova, Zuzana Molcanova, Magdalena Strečkova and Lubomir Medvecky
Inorganics 2021, 9(10), 77; https://doi.org/10.3390/inorganics9100077 - 15 Oct 2021
Cited by 6 | Viewed by 3150
Abstract
This study presents the synthesis, structural and luminescence properties for lanthanide metal–organic frameworks (LnMOFs), which belong to the sub-class of coordination polymers. The series of nanosized LnMOFs (Ln = Eu, Gd, Tb, Eu0.5Gd0.5, Tb0.5Gd0.5 and Eu [...] Read more.
This study presents the synthesis, structural and luminescence properties for lanthanide metal–organic frameworks (LnMOFs), which belong to the sub-class of coordination polymers. The series of nanosized LnMOFs (Ln = Eu, Gd, Tb, Eu0.5Gd0.5, Tb0.5Gd0.5 and Eu0.5Tb0.5) was prepared by solvothermal synthesis using a modulator (sodium acetate). We investigated the various surface chemistry compositions of the isostructural LnMOFs with a [Ln(btc)] structure (BTC: Benzene-1,3,5-tricarboxylate) by X-ray photoelectron spectroscopy (XPS). The XPS confirmed the mixed-valent Eu3+ and Eu2+ compounds, and the presence of Tb in both +3 and +4 valence states, and one +3 valency of Gd. A nanostructure of mixed LnMOFs (EuGd, TbGd and EuTb) with a rod-like shape is related to luminescence properties. The MOFs (EuTb and EuGd) presented Comission Internationale de l’Éclairage (CIE) chromaticities of x = 0.666 and y = 0.331, and x = 0.654 and y = 0.348, respectively, in the red region. They were better than the values desired for use in commercial phosphors, which are x = 0.64 and y = 0.35. For [Tb/Gd(btc)], the CIE coordinates were x = 0.334 and y = 0.562, presenting emissions in the green region. Bimetallic LnMOFs are very promising UV light sensors for biological applications. Full article
(This article belongs to the Special Issue Metal-Organic Frameworks: A Diverse Class of Compounds with Structures and Applications Only Limited by the Imagination of the Researcher)
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