Special Issue "Functional Coordination Polymers and Metal–Organic Frameworks"

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

Deadline for manuscript submissions: closed (30 April 2020).

Special Issue Editor

Dr. Andrea Rossin
Website SciProfiles
Guest Editor
Consiglio Nazionale delle Ricerche − Istituto di Chimica dei Composti Organometallici (ICCOM-CNR), Sesto Fiorentino (Firenze), Italy
Interests: Thiazole- and pyrazole-based CPs/MOFs synthesis and solid-state characterization; luminescent sensing; CO2 storage and conversion into added-value chemicals

Special Issue Information

Dear Colleagues,

Coordination Polymers (CPs) and Metal–Organic Frameworks (MOFs) are at the core of contemporary research on inorganic materials. The virtually infinite combination of their building blocks—inorganic metallic nodes (single ions or clusters) and organic polytopic linkers (polycarboxylates, bridging N-/S-/O-containing heterocycles)—generates solid air- and water-stable compounds. Interesting features from an applicative point of view are porosity, large surface area, and lattice flexibility (the “breathing” effect). These properties make them ubiquitous in several fields of materials science: gas storage and separation, luminescent sensing, heterogeneous catalysis, and magnetism. This Special Issue aims to collect full papers/critical reviews on the topic, possibly covering all the aforementioned applicative contexts. Scientific productions of both experimental and computational nature are welcome.

Dr. Andrea Rossin
Guest Editor

Manuscript Submission Information

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Keywords

  • coordination polymers
  • metal–organic frameworks
  • gas storage and separation
  • heterogeneous catalysis
  • magnetism
  • luminescent sensing

Published Papers (6 papers)

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Research

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Open AccessArticle
Adsorption Properties of Ce5(BDC)7.5(DMF)4 MOF
Inorganics 2020, 8(2), 9; https://doi.org/10.3390/inorganics8020009 - 26 Jan 2020
Cited by 1
Abstract
In this article we report on the spectroscopic and adsorptive studies done on Ce(III)-based MOF possessing, upon desolvation, open metal sites, and a discrete surface area. The Ce-based MOF was synthesized from terephthalic acid linker (H2BDC) and Ce3+ cations by [...] Read more.
In this article we report on the spectroscopic and adsorptive studies done on Ce(III)-based MOF possessing, upon desolvation, open metal sites, and a discrete surface area. The Ce-based MOF was synthesized from terephthalic acid linker (H2BDC) and Ce3+ cations by the classical solvothermal method. Preliminary powder X-ray diffraction analysis showed that the obtained materials corresponded to the ones reported by other authors. Spectroscopic techniques, such as XAS and in situ FTIR with probe molecules were used. In situ FTIR spectroscopy confirmed the successful removal of DMF molecules within the pore system at temperatures above 250 °C. Moreover, the use of CO as a probe molecule evidenced the presence of a Ce3+ open metal sites. Detailed volumetric and calorimetric CO2 adsorption studies are also reported. Full article
(This article belongs to the Special Issue Functional Coordination Polymers and Metal–Organic Frameworks)
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Open AccessArticle
Post Synthetic Defect Engineering of UiO-66 Metal–Organic Framework with An Iridium(III)-HEDTA Complex and Application in Water Oxidation Catalysis
Inorganics 2019, 7(10), 123; https://doi.org/10.3390/inorganics7100123 - 10 Oct 2019
Cited by 2
Abstract
Clean production of renewable fuels is a great challenge of our scientific community. Iridium complexes have demonstrated a superior catalytic activity in the water oxidation (WO) reaction, which is a crucial step in water splitting process. Herein, we have used a defective zirconium [...] Read more.
Clean production of renewable fuels is a great challenge of our scientific community. Iridium complexes have demonstrated a superior catalytic activity in the water oxidation (WO) reaction, which is a crucial step in water splitting process. Herein, we have used a defective zirconium metal–organic framework (MOF) with UiO-66 structure as support of a highly active Ir complex based on EDTA with the formula [Ir(HEDTA)Cl]Na. The defects are induced by the partial substitution of terephthalic acid with smaller formate groups. Anchoring of the complex occurs through a post-synthetic exchange of formate anions, coordinated at the zirconium clusters of the MOF, with the free carboxylate group of the [Ir(HEDTA)Cl] complex. The modified material was tested as a heterogeneous catalyst for the WO reaction by using cerium ammonium nitrate (CAN) as the sacrificial agent. Although turnover frequency (TOF) and turnover number (TON) values are comparable to those of other iridium heterogenized catalysts, the MOF exhibits iridium leaching not limited at the first catalytic run, as usually observed, suggesting a lack of stability of the hybrid system under strong oxidative conditions. Full article
(This article belongs to the Special Issue Functional Coordination Polymers and Metal–Organic Frameworks)
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Open AccessArticle
An Optimised Compaction Process for Zr-Fumarate (MOF-801)
Inorganics 2019, 7(9), 110; https://doi.org/10.3390/inorganics7090110 - 05 Sep 2019
Cited by 1
Abstract
We reported a systematic approach aimed at identifying the optimal conditions for compaction of MOF-801, a small-pore zirconium-based metal–organic framework (MOF) containing fumaric acid as the linker, that can be easily synthesised in aqueous medium. Pellets of the MOF were prepared by compressing [...] Read more.
We reported a systematic approach aimed at identifying the optimal conditions for compaction of MOF-801, a small-pore zirconium-based metal–organic framework (MOF) containing fumaric acid as the linker, that can be easily synthesised in aqueous medium. Pellets of the MOF were prepared by compressing the powder either in neat form or dry-mixed with binders (sucrose, polyvinylalcohol, polyvinylbutyral) under a range of pressures and for different times. The mechanical stability and durability of the pellets was tested by simple drop tests and shake tests, finding that addition of 5% of polyvinylbutyral was enough to produce highly resilient pellets that did not release significant amounts of powder upon cracking. The crystallinity, textural properties and CO2 adsorption performance of the MOF were successively assessed, observing the least change of the original properties in pellets compressed at 146 MPa for 15 s. Compaction at higher pressures impacted the performance more heavily, with no evident benefit from the mechanical point of view, whereas compression time did not have a relevant effect. The cyclic adsorption behaviour was tested, showing that the pellets retained as much as 90% of the CO2 working capacity, while displaying unaffected sorption kinetics, and 74% of the H2O working capacity. Full article
(This article belongs to the Special Issue Functional Coordination Polymers and Metal–Organic Frameworks)
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Open AccessArticle
Effect of Coordinating Solvents on the Structure of Cu(II)-4,4′-bipyridine Coordination Polymers
Inorganics 2019, 7(8), 103; https://doi.org/10.3390/inorganics7080103 - 19 Aug 2019
Cited by 1
Abstract
Solvent can play a crucial role in the synthesis of coordination polymers (CPs). Here, this study reports how the coordinating solvent approach (CSA) can be used as an effective tool to control the nature of the final CP. This study exploited the system [...] Read more.
Solvent can play a crucial role in the synthesis of coordination polymers (CPs). Here, this study reports how the coordinating solvent approach (CSA) can be used as an effective tool to control the nature of the final CP. This study exploited the system Cu(II)-4,4′-bipyridine coupled to different coordinating solvents, such as DMA, DMF and DMSO. This allowed the isolation and structurally characterization of four new CPs: three 2D layered networks and one 1D chain. Moreover, it was evidenced that even adventitious water can play the role of the coordinating solvent in the final CP. Full article
(This article belongs to the Special Issue Functional Coordination Polymers and Metal–Organic Frameworks)
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Open AccessArticle
Green Synthesis of a Functionalized Zirconium-Based Metal–Organic Framework for Water and Ethanol Adsorption
Inorganics 2019, 7(5), 56; https://doi.org/10.3390/inorganics7050056 - 26 Apr 2019
Cited by 5
Abstract
Aqueous synthesis of metal–organic frameworks (MOFs) at room temperature offers many advantages such as reduction in the generation of toxic byproducts and operation costs, as well as increased safety in the material’s production. Functional group-bearing MOFs have received growing attention compared to nonfunctionalized [...] Read more.
Aqueous synthesis of metal–organic frameworks (MOFs) at room temperature offers many advantages such as reduction in the generation of toxic byproducts and operation costs, as well as increased safety in the material’s production. Functional group-bearing MOFs have received growing attention compared to nonfunctionalized analogues due to enhanced adsorption properties of the former in many cases. Here, we report an aqueous solution-based synthesis of a robust zirconium MOF, UiO-66-NO2, at room temperature. We evaluated the phase purity, porosity, thermal stability, particle morphology and size of the resulting material. High uptake, as well as near complete recyclability of water and ethanol vapor isotherms at room temperature supports the potential of UiO-66-NO2 as a solid adsorbent in adsorption-based cooling applications or water harvesting systems. Full article
(This article belongs to the Special Issue Functional Coordination Polymers and Metal–Organic Frameworks)
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Review

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Open AccessReview
Thiazole- and Thiadiazole-Based Metal–Organic Frameworks and Coordination Polymers for Luminescent Applications
Inorganics 2019, 7(12), 144; https://doi.org/10.3390/inorganics7120144 - 14 Dec 2019
Cited by 4
Abstract
This mini-review focuses on the 2015–2019 literature survey of thiazole- and thiadiazole-containing Metal–Organic Frameworks (MOFs) and Coordination Polymers (CPs) exploited in the applicative field of luminescent sensing. Full article
(This article belongs to the Special Issue Functional Coordination Polymers and Metal–Organic Frameworks)
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