Special Issue "Metal Phosphonates and Phosphinates"

A special issue of Crystals (ISSN 2073-4352). This special issue belongs to the section "Crystalline Materials".

Deadline for manuscript submissions: closed (30 April 2019).

Special Issue Editors

Guest Editor
Dr. Marco Taddei

Energy Safety Research Institute, College of Engineering, Swansea University - Bay Campus Fabian Way, Swansea, SA1 8EN, UK
Website | E-Mail
Interests: carbon dioxide capture; materials chemistry; metal-organic frameworks; powder X-ray diffraction
Guest Editor
Dr. Ferdinando Costantino

Department of Chemistry Biology and Biotechnologies, University of Perugia, Via Elce di Sotto n. 8 06127 Perugia, Italy
Website | E-Mail
Interests: layered materials; metal-organic frameworks; X-ray diffraction; catalysis

Special Issue Information

Dear Colleagues,

We are pleased to announce the forthcoming “1st European Workshop on Metal Phosphonates Chemistry—Materials for Energy Applications and Beyond”, which will be held at the Energy Safety Research Institute (ESRI)—Swansea University, on 19 September, 2018, and to invite you to contribute to the present joint Special Issue of Crystals entitled “Metal Phosphonates and Phosphinates”.

Metal phosphonates and phosphinates (MPPs) are a class of crystalline metal–organic compounds characterized by a fascinating coordination chemistry and vast structural diversity. These materials display exceptional thermal and chemical stability, which makes them attractive for practical applications.

The scope of the “1st European Workshop on Metal Phosphonates Chemistry—Materials for Energy Applications and Beyond” is to bring together, for the first time, researchers from across Europe working in the field of metal phosphonates and phosphinates to discuss about the latest advancements and future directions. The scientific program covers a broad range of topics, such as synthesis, advanced methods for characterisation, porous materials, molecular magnetic compounds, energy storage and heterogeneous catalysis. For more information about the workshop, please visit the following link: https://europhosphonates.wordpress.com/

Submission of original research papers or reviews to this Special Issue of Crystals is open for both participants of the workshop and other researchers working in the field of metal phosphonates and phosphinates.


Dr. Marco Taddei
Dr. Ferdinando Costantino
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 papers will be 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. Crystals 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 1400 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.

Published Papers (6 papers)

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Research

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Open AccessArticle
Novel Cerium Bisphosphinate Coordination Polymer and Unconventional Metal–Organic Framework
Crystals 2019, 9(6), 303; https://doi.org/10.3390/cryst9060303
Received: 30 April 2019 / Revised: 7 June 2019 / Accepted: 7 June 2019 / Published: 12 June 2019
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Abstract
The first Ce(III)-based coordination polymer ICR-9 (ICR stands for Inorganic Chemistry Řež), with the formula Ce2(C8H10P2O4)3, containing ditopic phenylene-1,4-bis(methylphosphinic acid) linker, was synthetized under solvothermal conditions. The crystal structure, solved using [...] Read more.
The first Ce(III)-based coordination polymer ICR-9 (ICR stands for Inorganic Chemistry Řež), with the formula Ce2(C8H10P2O4)3, containing ditopic phenylene-1,4-bis(methylphosphinic acid) linker, was synthetized under solvothermal conditions. The crystal structure, solved using electron diffraction tomography (EDT), revealed 2D layers of octahedrally coordinated cerium atoms attached together through O-P-O bridges. The structure is nonporous, however, the modification of synthetic conditions led to unconventional metal–organic framework (or defective amorphous phase) with a specific surface area up to approximately 400 m2 g-1. Full article
(This article belongs to the Special Issue Metal Phosphonates and Phosphinates)
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Open AccessArticle
Platonic Relationships in Metal Phosphonate Chemistry: Ionic Metal Phosphonates
Crystals 2019, 9(6), 301; https://doi.org/10.3390/cryst9060301
Received: 15 May 2019 / Revised: 3 June 2019 / Accepted: 7 June 2019 / Published: 11 June 2019
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Abstract
Phosphonate ligands demonstrate strong affinity for metal ions. However, there are several cases where the phosphonate is found non-coordinated to the metal ion. Such compounds could be characterized as salts, since the interactions involved are ionic and hydrogen bonding. In this paper we [...] Read more.
Phosphonate ligands demonstrate strong affinity for metal ions. However, there are several cases where the phosphonate is found non-coordinated to the metal ion. Such compounds could be characterized as salts, since the interactions involved are ionic and hydrogen bonding. In this paper we explore a number of such examples, using divalent metal ions (Mg2+, Ca2+, Sr2+ and Ni2+) and the phosphonic acids: p-aminobenzylphosphonic acid (H2PABPA), tetramethylenediamine-tetrakis(methylenephosphonic acid) (H8TDTMP), and 1,2-ethylenediphosphonic acid (H4EDPA). The compounds isolated and structurally characterized are [Mg(H2O)6]·[HPABPA]2·6H2O, [Ca(H2O)8]·[HPABPA]2, [Sr(H2O)8]·[HPABPA]2, [Mg(H2O)6]·[H6TDTMP], and [Ni(H2O)6]·[H2EDPA]·H2O. Also, the coordination polymer {[Ni(4,4’-bpy)(H2O)4]·[H2EDPA]·H2O}n was synthesized and characterized, which contains a bridging 4,4’-bipyridine (4,4’-bpy) ligand forming an infinite chain with the Ni2+ cations. All these compounds contain the phosphonate anion as the counterion to charge balance the cationic charge originating from the metal cation. Full article
(This article belongs to the Special Issue Metal Phosphonates and Phosphinates)
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Open AccessArticle
Mechanochemical Access to Elusive Metal Diphosphinate Coordination Polymer
Crystals 2019, 9(6), 283; https://doi.org/10.3390/cryst9060283
Received: 24 April 2019 / Revised: 21 May 2019 / Accepted: 25 May 2019 / Published: 29 May 2019
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Abstract
Several binary metal diphosphinate compounds (ML) have been reported for diphosphinate bonded by a single methylene fragment. In case of longer bridges, binary products are difficult to isolate in crystalline form. Here, using a solvent assisted mechano-chemistry synthesis, we report two new ML [...] Read more.
Several binary metal diphosphinate compounds (ML) have been reported for diphosphinate bonded by a single methylene fragment. In case of longer bridges, binary products are difficult to isolate in crystalline form. Here, using a solvent assisted mechano-chemistry synthesis, we report two new ML crystalline phases, one hydrated and one anhydrous. The hydrated phase is a 2D coordination polymer with an open framework structure. Its network displays a new topology for coordination polymers and metal organic frameworks. The thermal behavior of the two phases has been studied. Finally, the importance of the bridge length is discussed in view of known metal diphosphinate compounds. Full article
(This article belongs to the Special Issue Metal Phosphonates and Phosphinates)
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Open AccessArticle
Where Are the tpy Embraces in [Zn{4′-(EtO)2OPC6H4tpy}2][CF3SO3]2?
Crystals 2018, 8(12), 461; https://doi.org/10.3390/cryst8120461
Received: 28 November 2018 / Revised: 7 December 2018 / Accepted: 7 December 2018 / Published: 10 December 2018
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Abstract
In this paper, the bromo- and phosphonate-ester-functionalized complexes [Zn(1)2][CF3SO3]2 and [Zn(2)2][CF3SO3]2 (1 = 4′-(4-bromophenyl)-2,2′:6′,2″-terpyridine, 2 = diethyl (4-([2,2′:6′,2″-terpyridin]-4′-yl)phenyl)phosphonate) are reported. The complexes have been [...] Read more.
In this paper, the bromo- and phosphonate-ester-functionalized complexes [Zn(1)2][CF3SO3]2 and [Zn(2)2][CF3SO3]2 (1 = 4′-(4-bromophenyl)-2,2′:6′,2″-terpyridine, 2 = diethyl (4-([2,2′:6′,2″-terpyridin]-4′-yl)phenyl)phosphonate) are reported. The complexes have been characterized by electrospray mass spectrometry, IR and absorption spectroscopies, and multinuclear NMR spectroscopy. The single-crystal structures of [Zn(1)2][CF3SO3]2.MeCN.1/2Et2O and [Zn(2)2][CF3SO3]2 have been determined and they confirm {Zn(tpy)2}2+ cores (tpy = 2,2′:6′,2″-terpyridine). Ongoing from X = Br to P(O)(OEt)2, the {Zn(4′-XC6H4tpy)2}2+ unit exhibits significant “bowing” of the backbone, which is associated with changes in packing interactions. The [Zn(1)2]2+ cations engage in head-to-tail 4′-Phtpy...4′-Phtpy embraces with efficient pyridine...phenylene π-stacking interactions. The [Zn(2)2]2+ cations pack with one of the two ligands involved in pyridine...pyridine π-stacking; steric hindrance between one C6H4PO(OEt)2 group and an adjacent pair of π-stacked pyridine rings results in distortion of backbone of the ligand. This report is the first crystallographic determination of a salt of a homoleptic [M{4′-(RO)2OPC6H4tpy}2]n+ cation. Full article
(This article belongs to the Special Issue Metal Phosphonates and Phosphinates)
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Open AccessArticle
A Phosphonic Acid Anchoring Analogue of the Sensitizer P1 for p-Type Dye-Sensitized Solar Cells
Crystals 2018, 8(10), 389; https://doi.org/10.3390/cryst8100389
Received: 18 September 2018 / Revised: 5 October 2018 / Accepted: 9 October 2018 / Published: 12 October 2018
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Abstract
We report the synthesis and characterization of the first example of an organic dye, PP1, for p-type dye-sensitized solar cells (DSCs) bearing a phosphonic acid anchoring group. PP1 is structurally related to the benchmarking dye, P1, which possesses a carboxylic acid [...] Read more.
We report the synthesis and characterization of the first example of an organic dye, PP1, for p-type dye-sensitized solar cells (DSCs) bearing a phosphonic acid anchoring group. PP1 is structurally related to the benchmarking dye, P1, which possesses a carboxylic acid anchor. The solution absorption spectra of PP1 and P1 are similar (PP1 has λmax = 478 nm and εmax = 62,800 dm3 mol−1 cm−1), as are the solid-state absorption spectra of the dyes adsorbed on FTO/NiO electrodes. p-Type DSCs with NiO as semiconductor and sensitized with P1 or PP1 perform comparably. For PP1, short-circuit current densities (JSC) and open-circuit voltages (VOC) for five DSCs lie between 1.11 and 1.45 mA cm−2, and 119 and 143 mV, respectively, compared to ranges of 1.55–1.80 mA cm−2 and 117–130 mV for P1. Photoconversion efficiencies with PP1 are in the range 0.054–0.069%, compared to 0.065–0.079% for P1. Electrochemical impedance spectroscopy, open-circuit photovoltage decay and intensity-modulated photocurrent spectroscopy have been used to compare DSCs with P1 and PP1 in detail. Full article
(This article belongs to the Special Issue Metal Phosphonates and Phosphinates)
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Open AccessPerspective
New Directions in Metal Phosphonate and Phosphinate Chemistry
Crystals 2019, 9(5), 270; https://doi.org/10.3390/cryst9050270
Received: 30 April 2019 / Revised: 20 May 2019 / Accepted: 21 May 2019 / Published: 24 May 2019
Cited by 3 | PDF Full-text (15919 KB) | HTML Full-text | XML Full-text
Abstract
In September 2018, the First European Workshop on Metal Phosphonates Chemistry brought together some prominent researchers in the field of metal phosphonates and phosphinates with the aim of discussing past and current research efforts and identifying future directions. The scope of this perspective [...] Read more.
In September 2018, the First European Workshop on Metal Phosphonates Chemistry brought together some prominent researchers in the field of metal phosphonates and phosphinates with the aim of discussing past and current research efforts and identifying future directions. The scope of this perspective article is to provide a critical overview of the topics discussed during the workshop, which are divided into two main areas: synthesis and characterisation, and applications. In terms of synthetic methods, there has been a push towards cleaner and more efficient approaches. This has led to the introduction of high-throughput synthesis and mechanochemical synthesis. The recent success of metal–organic frameworks has also promoted renewed interest in the synthesis of porous metal phosphonates and phosphinates. Regarding characterisation, the main advances are the development of electron diffraction as a tool for crystal structure determination and the deployment of in situ characterisation techniques, which have allowed for a better understanding of reaction pathways. In terms of applications, metal phosphonates have been found to be suitable materials for several purposes: they have been employed as heterogeneous catalysts for the synthesis of fine chemicals, as solid sorbents for gas separation, notably CO2 capture, as materials for electrochemical devices, such as fuel cells and rechargeable batteries, and as matrices for drug delivery. Full article
(This article belongs to the Special Issue Metal Phosphonates and Phosphinates)
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