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Inorganics
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Functional Coordination Polymers and Metal–Organic Frameworks
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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 (31 October 2020) | Viewed by 57409

Printed Edition Available!
A printed edition of this Special Issue is available here.

Special Issue Editor

Dr. Andrea Rossin

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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 Issues, Collections and Topics in MDPI journals

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

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Keywords

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

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Published Papers (11 papers)

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Editorial

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4 pages, 437 KiB  
Editorial
Editorial for Special Issue “Functional Coordination Polymers and Metal–Organic Frameworks”
by Andrea Rossin
Inorganics 2021, 9(5), 33; https://doi.org/10.3390/inorganics9050033 - 3 May 2021
Viewed by 2240
Abstract
Metal–Organic Frameworks (MOFs) and Coordination Polymers (CPs) are at the forefront of contemporary coordination chemistry research, as witnessed by the impressive (and ever-growing) number of publications appearing in the literature on this topic in the last 20 years (Figure 1), reaching almost 4000 [...] Read more.
Metal–Organic Frameworks (MOFs) and Coordination Polymers (CPs) are at the forefront of contemporary coordination chemistry research, as witnessed by the impressive (and ever-growing) number of publications appearing in the literature on this topic in the last 20 years (Figure 1), reaching almost 4000 papers in 2020 [...] Full article
(This article belongs to the Special Issue Functional Coordination Polymers and Metal–Organic Frameworks)
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Figure 1

Research

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12 pages, 3253 KiB  
Article
Photoluminescent Coordination Polymers Based on Group 12 Metals and 1H-Indazole-6-Carboxylic Acid
by Antonio A. García-Valdivia, Estitxu Echenique-Errandonea, Gloria B. Ramírez-Rodríguez, José M. Delgado-López, Belén Fernández, Sara Rojas, Javier Cepeda and Antonio Rodríguez-Diéguez
Inorganics 2021, 9(3), 20; https://doi.org/10.3390/inorganics9030020 - 22 Mar 2021
Cited by 6 | Viewed by 3207
Abstract
Two new coordination polymers (CPs) based on Zn(II) and Cd(II) and 1H-indazole-6-carboxylic acid (H2L) of general formulae [Zn(L)(H2O)]n (1) and [Cd2(HL)4]n (2) have been synthesized and fully [...] Read more.
Two new coordination polymers (CPs) based on Zn(II) and Cd(II) and 1H-indazole-6-carboxylic acid (H2L) of general formulae [Zn(L)(H2O)]n (1) and [Cd2(HL)4]n (2) have been synthesized and fully characterized by elemental analyses, Fourier transformed infrared spectroscopy and single crystal X-ray diffraction. The results indicate that compound 1 possesses double chains in its structure whereas 2 exhibits a 3D network. The intermolecular interactions, including hydrogen bonds, C–H···π and π···π stacking interactions, stabilize both crystal structures. Photoluminescence (PL) properties have shown that compounds 1 and 2 present similar emission spectra compared to the free-ligand. The emission spectra are also studied from the theoretical point of view by means of time-dependent density-functional theory (TD-DFT) calculations to confirm that ligand-centred π-π* electronic transitions govern emission of compound 1 and 2. Finally, the PL properties are also studied in aqueous solution to explore the stability and emission capacity of the compounds. Full article
(This article belongs to the Special Issue Functional Coordination Polymers and Metal–Organic Frameworks)
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19 pages, 5158 KiB  
Article
New Coordination Polymers of Zinc(II), Copper(II) and Cadmium(II) with 1,3-Bis(1,2,4-triazol-4-yl)adamantane
by Nertil Xhaferaj, Aurel Tăbăcaru, Marco Moroni, Ganna A. Senchyk, Kostiantyn V. Domasevitch, Claudio Pettinari and Simona Galli
Inorganics 2020, 8(11), 60; https://doi.org/10.3390/inorganics8110060 - 6 Nov 2020
Cited by 6 | Viewed by 3022
Abstract
The new coordination polymers (CPs) [Zn(tr2ad)Cl2]n, {[Cu(tr2ad)Cl]Cl∙4H2O}n, [Cd2(tr2ad)Cl4]n, {[Cu(tr2ad)(NO3)](NO3)}n and {[Cd(tr2ad)(NO3)](NO3 [...] Read more.
The new coordination polymers (CPs) [Zn(tr2ad)Cl2]n, {[Cu(tr2ad)Cl]Cl∙4H2O}n, [Cd2(tr2ad)Cl4]n, {[Cu(tr2ad)(NO3)](NO3)}n and {[Cd(tr2ad)(NO3)](NO3)∙H2O}n were obtained in the form of air- and moisture-stable microcrystalline powders by the solvothermal reactions of zinc(II), copper(II) and cadmium(II) chlorides or nitrates with the ligand 1,3-bis(1,2,4-triazol-4-yl)adamantane (tr2ad). Investigation of the thermal behaviour assessed the thermal stability of these CPs, with [Cd2(tr2ad)Cl4]n starting to decompose only around 365 °C. As retrieved by powder X-ray diffraction, while [Zn(tr2ad)Cl2]n features 1-D chains along which the metal centre shows a tetrahedral geometry and the spacer is exo-bidentate, the other CPs contain 2-D double-layers in which the metal ions possess an octahedral stereochemistry and the linker is exo-tetradentate. A comparative structural analysis involving known coordination compounds containing the tr2ad ligand enabled us to disclose (i) the versatility of the ligand, as far as the coordination modes are concerned; (ii) the variability in crystal structure dimensionality, ranging from 1-D to 3-D; (iii) the fact that, to the best of our knowledge, [Zn(tr2ad)Cl2]n is the first ZnII-based CP containing the tr2ad spacer. Full article
(This article belongs to the Special Issue Functional Coordination Polymers and Metal–Organic Frameworks)
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12 pages, 2752 KiB  
Article
Synthesis and Thermochromic Luminescence of Ag(I) Complexes Based on 4,6-Bis(diphenylphosphino)-Pyrimidine
by Alexander V. Artem’ev, Maria P. Davydova, Alexey S. Berezin and Denis G. Samsonenko
Inorganics 2020, 8(9), 46; https://doi.org/10.3390/inorganics8090046 - 26 Aug 2020
Cited by 11 | Viewed by 3328
Abstract
Two Ag(I)-based metal-organic compounds have been synthesized exploiting 4,6-bis(diphenylphosphino)pyrimidine (L). The reaction of this ligand with AgNO3 and AgBF4 in acetonitrile produces dinuclear complex, [Ag2L2(MeCN)2(NO3)2] (1) and 1D coordination [...] Read more.
Two Ag(I)-based metal-organic compounds have been synthesized exploiting 4,6-bis(diphenylphosphino)pyrimidine (L). The reaction of this ligand with AgNO3 and AgBF4 in acetonitrile produces dinuclear complex, [Ag2L2(MeCN)2(NO3)2] (1) and 1D coordination polymer, [Ag2L(MeCN)3]n(BF4)2n (2), respectively. In complex 1, µ2-P,P′-bridging coordination pattern of the ligand L is observed, whereas its µ4-P,N,N′,P′-coordination mode appears in 2. Both compounds exhibit pronounced thermochromic luminescence expressed by reversible changing of the emission chromaticity from a yellow at 300 K to an orange at 77 K. At room temperature, the emission lifetimes of 1 and 2 are 15.5 and 9.4 µs, the quantum efficiency being 18 and 56%, respectively. On account of temperature-dependent experimental data, the phenomenon was tentatively ascribed to alteration of the emission nature from thermally activated delayed fluorescence at 300 K to phosphoresce at 77 K. Full article
(This article belongs to the Special Issue Functional Coordination Polymers and Metal–Organic Frameworks)
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10 pages, 2595 KiB  
Article
Adsorption Properties of Ce5(BDC)7.5(DMF)4 MOF
by Cesare Atzori, Jayashree Ethiraj, Valentina Colombo, Francesca Bonino and Silvia Bordiga
Inorganics 2020, 8(2), 9; https://doi.org/10.3390/inorganics8020009 - 26 Jan 2020
Cited by 13 | Viewed by 4236
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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12 pages, 1929 KiB  
Article
Post Synthetic Defect Engineering of UiO-66 Metal–Organic Framework with An Iridium(III)-HEDTA Complex and Application in Water Oxidation Catalysis
by Giordano Gatto, Alceo Macchioni, Roberto Bondi, Fabio Marmottini and Ferdinando Costantino
Inorganics 2019, 7(10), 123; https://doi.org/10.3390/inorganics7100123 - 10 Oct 2019
Cited by 10 | Viewed by 5205
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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12 pages, 5697 KiB  
Article
An Optimised Compaction Process for Zr-Fumarate (MOF-801)
by Marco Taddei, Matthew J. McPherson, Abel Gougsa, Jamie Lam, Jack Sewell and Enrico Andreoli
Inorganics 2019, 7(9), 110; https://doi.org/10.3390/inorganics7090110 - 5 Sep 2019
Cited by 19 | Viewed by 7976
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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10 pages, 7418 KiB  
Article
Effect of Coordinating Solvents on the Structure of Cu(II)-4,4′-bipyridine Coordination Polymers
by Marzio Rancan, Alice Carlotto, Gregorio Bottaro and Lidia Armelao
Inorganics 2019, 7(8), 103; https://doi.org/10.3390/inorganics7080103 - 19 Aug 2019
Cited by 8 | Viewed by 4313
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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9 pages, 1593 KiB  
Article
Green Synthesis of a Functionalized Zirconium-Based Metal–Organic Framework for Water and Ethanol Adsorption
by Zhijie Chen, Xingjie Wang, Timur Islamoglu and Omar K. Farha
Inorganics 2019, 7(5), 56; https://doi.org/10.3390/inorganics7050056 - 26 Apr 2019
Cited by 27 | Viewed by 7092
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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26 pages, 4981 KiB  
Review
Metal–Organic Frameworks as Versatile Platforms for Organometallic Chemistry
by Fan Chen, Hannah F. Drake, Liang Feng, Joshua A. Powell, Kun-Yu Wang, Tian-Hao Yan and Hong-Cai Zhou
Inorganics 2021, 9(4), 27; https://doi.org/10.3390/inorganics9040027 - 9 Apr 2021
Cited by 18 | Viewed by 9033
Abstract
Metal–organic frameworks (MOFs) are emerging porous materials with highly tunable structures developed in the 1990s, while organometallic chemistry is of fundamental importance for catalytic transformation in the academic and industrial world for many decades. Through the years, organometallic chemistry has been incorporated into [...] Read more.
Metal–organic frameworks (MOFs) are emerging porous materials with highly tunable structures developed in the 1990s, while organometallic chemistry is of fundamental importance for catalytic transformation in the academic and industrial world for many decades. Through the years, organometallic chemistry has been incorporated into functional MOF construction for diverse applications. Here, we will focus on how organometallic chemistry is applied in MOF design and modifications from linker-centric and metal-cluster-centric perspectives, respectively. Through structural design, MOFs can function as a tailorable platform for traditional organometallic transformations, including reaction of alkenes, cross-coupling reactions, and C–H activations. Besides, an overview will be made on other application categories of organometallic MOFs, such as gas adsorption, magnetism, quantum computing, and therapeutics. Full article
(This article belongs to the Special Issue Functional Coordination Polymers and Metal–Organic Frameworks)
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16 pages, 4351 KiB  
Review
Thiazole- and Thiadiazole-Based Metal–Organic Frameworks and Coordination Polymers for Luminescent Applications
by Giorgio Mercuri, Giuliano Giambastiani and Andrea Rossin
Inorganics 2019, 7(12), 144; https://doi.org/10.3390/inorganics7120144 - 14 Dec 2019
Cited by 27 | Viewed by 5713
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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