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Coordination Polymers: Synthesis, Crystal Structure and Multifunctional Applications
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Coordination Polymers: Synthesis, Crystal Structure and Multifunctional Applications

A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: closed (20 January 2022) | Viewed by 19474

Special Issue Editor

Prof. Dr. Andrei S. Potapov

E-Mail Website
Guest Editor
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3 Lavrentiev Ave., 630090 Novosibirsk, Russia
Interests: nitrogen ligands; metal–organic frameworks; luminescence
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Coordination polymers are constructed from metal ions and bridging ligands, which join them into infinite 1D chains or 2D and 3D networks. Chemistry coordination polymers is a vibrant field of modern science, which is confirmed by an exponential increase in the number of scientific articles, reviews, and thematic issues in the best journals. A wide variety of possible coordination arrangements of metal ions and geometries of linkers provides almost unlimited possibilities for constructing coordination polymers of various topologies. The functional properties of coordination polymers can be modified by introducing various functional groups into organic linkers, which affect sorption, catalytic, photophysical, and other properties. The presence of a developed system of pores and channels in the structure of coordinatin polymers provides high values of sorption capacity and selectivity for industrially important gases and their mixtures—hydrogen, carbon dioxide, water vapor, methane, ethane, ethylene, and acetylene. Another important characteristic of coordination polymers is their luminescent properties, which can be associated with various types of electronic transitions—intraligand, metal-centered, metal–ligand, and ligand–metal charge transfer. Electronic transitions in guest molecules included in the pores of the framework are also possible. The photophysical properties of coordination polymers are used to create electroluminescent materials for LEDs, as contrast agents in biomedical imaging, theranostics, and photodynamic therapy.

The aim of current Special Issue is to cover various aspects of the synthesis, structural characterization, and study of functional properties of both inorganic and metal-organic coordination polymers. It is our pleasure to invite you to submit communications, full papers, and reviews for this Special Issue.

Prof. Andrei S. Potapov
Guest Editor

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. Materials is an international peer-reviewed open access semimonthly 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 2600 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

  • coordination network
  • metal-organic framework
  • catalysis
  • luminescence
  • topology
  • gas sorption
  • coordination polymer

Published Papers (6 papers)

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Research

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16 pages, 3204 KiB  
Article
New Coordination Polymers of Selected Lanthanides with 1,2-Phenylenediacetate Linker: Structures, Thermal and Luminescence Properties
by Renata Łyszczek, Iwona Rusinek, Agnieszka Ostasz, Justyna Sienkiewicz-Gromiuk, Dmytro Vlasyuk, Marcin Groszek, Agnieszka Lipke and Oleksiy Pavlyuk
Materials 2021, 14(17), 4871; https://doi.org/10.3390/ma14174871 - 27 Aug 2021
Cited by 6 | Viewed by 1896
Abstract
Solvothermal reactions of lanthanide (III) salts with 1,2-phenylenediacetic acid in N,N′-dimethylformamide (DMF) solvent lead to the formation of the metal complexes of the general formula Ln2(1,2-pda)3(DMF)2, where Ln(III) = Pr(1), Sm(2 [...] Read more.
Solvothermal reactions of lanthanide (III) salts with 1,2-phenylenediacetic acid in N,N′-dimethylformamide (DMF) solvent lead to the formation of the metal complexes of the general formula Ln2(1,2-pda)3(DMF)2, where Ln(III) = Pr(1), Sm(2), Eu(3), Tb(4), Dy(5), and Er(6), 1,2-pda = [C6H4(CH2COO)2]2−. The compounds were characterized by elemental analysis, powder and single-crystal X-ray diffraction methods, thermal analysis methods (TG-DSC and TG-FTIR), infrared and luminescence spectroscopy. They exhibit structural similarity in the two groups (Pr, Sm, and Eu; Tb, Dy, and Er), which was reflected in their thermal behaviours and spectroscopic properties. Single-crystal X-ray diffraction studies reveal that Sm(2) and Eu(3) complexes form 2D coordination polymers with four crystallographically independent metal centers. Every second lanthanide ion is additionally coordinated by two DMF molecules. The 1,2-phenylenediacetate linker shows different denticity being: penta- and hexadentate while carboxylate groups exhibit bidentate-bridging, bidentate-chelating, and three-dentate bridging-chelating modes. The infrared spectra reflect divergence between these two groups of complexes. The complexes of lighter lanthanides contain in the structure coordinated DMF molecules, while in the structures of heavier complexes, DMF molecules appear in the inner and outer coordination sphere. Both carboxylate groups are deprotonated and engaged in the coordination of metal centers but in different ways in such groups of complexes. In the groups, the thermal decomposition of the isostructural complexes occurs similarly. Pyrolysis of complexes takes place with the formation of such gaseous products as DMF, carbon oxides, ortho-xylene, ethers, water, carboxylic acids, and esters. The complexes of Eu and Tb exhibit characteristic luminescence in the VIS region, while the erbium complex emits NIR wavelength. Full article
(This article belongs to the Special Issue Coordination Polymers: Synthesis, Crystal Structure and Multifunctional Applications)
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15 pages, 3247 KiB  
Article
Structural and Thermal Investigations of Co(II) and Ni(II) Coordination Polymers Based on biphenyl-4,4′-dioxydiacetate Linker
by Halina Głuchowska, Renata Łyszczek, Liliana Mazur and Alexander M. Kirillov
Materials 2021, 14(13), 3545; https://doi.org/10.3390/ma14133545 - 25 Jun 2021
Cited by 4 | Viewed by 1658
Abstract
Two coordination polymers, [Co(µ4-L)(H2O)2]n (1) and [Ni(µ-L)(H2O)4]n (2), were solvothermally assembled from the corresponding metal(II) chlorides and biphenyl-4,4-dioxydiacetic acid (H2L) as a flexible dicarboxylate linker. [...] Read more.
Two coordination polymers, [Co(µ4-L)(H2O)2]n (1) and [Ni(µ-L)(H2O)4]n (2), were solvothermally assembled from the corresponding metal(II) chlorides and biphenyl-4,4-dioxydiacetic acid (H2L) as a flexible dicarboxylate linker. The cobalt(II) compound 1 featured a layer-pillared 3D metal-organic network with a cds topology, while the nickel(II) derivative 2 represented a linear chain 1D coordination polymer with a 2C1 topology. The µ4− and µ-L2− linkers exhibited different denticity and coordination modes in the synthesized compounds, thus contributing to their structural diversity. The dimensionality of 1 and 2 had an influence on their thermal stability and decomposition processes, which were investigated in detail by TG-DSC and TG-FTIR methods. Thermal decomposition products of coordination polymers were also analyzed by PXRD, confirming the formation of Co3O4/CoO and NiO as final materials. The obtained compounds broaden a family of coordination polymers assembled from flexible dicarboxylate linkers. Full article
(This article belongs to the Special Issue Coordination Polymers: Synthesis, Crystal Structure and Multifunctional Applications)
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20 pages, 6426 KiB  
Article
Multidimensional Ln-Aminophthalate Photoluminescent Coordination Polymers
by Carla Queirós, Chen Sun, Ana M. G. Silva, Baltazar de Castro, Juan Cabanillas-Gonzalez and Luís Cunha-Silva
Materials 2021, 14(7), 1786; https://doi.org/10.3390/ma14071786 - 04 Apr 2021
Cited by 1 | Viewed by 2283
Abstract
The development of straightforward reproducible methods for the preparation of new photoluminescent coordination polymers (CPs) is an important goal in luminescence and chemical sensing fields. Isophthalic acid derivatives have been reported for a wide range of applications, and in addition to their relatively [...] Read more.
The development of straightforward reproducible methods for the preparation of new photoluminescent coordination polymers (CPs) is an important goal in luminescence and chemical sensing fields. Isophthalic acid derivatives have been reported for a wide range of applications, and in addition to their relatively low cost, have encouraged its use in the preparation of novel lanthanide-based coordination polymers (LnCPs). Considering that the photoluminescent properties of these CPs are highly dependent on the existence of water molecules in the crystal structure, our research efforts are now focused on the preparation of CP with the lowest water content possible, while considering a green chemistry approach. One- and two-dimensional (1D and 2D) LnCPs were prepared from 5-aminoisophthalic acid and Sm3+/Tb3+ using hydrothermal and/or microwave-assisted synthesis. The unprecedented LnCPs were characterized by single-crystal X-ray diffraction (SCRXD), powder X-ray diffraction (PXRD), Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopy (SEM), and their photoluminescence (PL) properties were studied in the solid state, at room temperature, using the CPs as powders and encapsulated in poly(methyl methacrylate (PMMA) films, envisaging the potential preparation of devices for sensing. The materials revealed interesting PL properties that depend on the dimensionality, metal ion, co-ligand used and water content. Full article
(This article belongs to the Special Issue Coordination Polymers: Synthesis, Crystal Structure and Multifunctional Applications)
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22 pages, 4508 KiB  
Article
Molecular and Polymer Ln2M2 (Ln = Eu, Gd, Tb, Dy; M = Zn, Cd) Complexes with Pentafluorobenzoate Anions: The Role of Temperature and Stacking Effects in the Structure; Magnetic and Luminescent Properties
by Maxim A. Shmelev, Mikhail A. Kiskin, Julia K. Voronina, Konstantin A. Babeshkin, Nikolay N. Efimov, Evgenia A. Varaksina, Vladislav M. Korshunov, Ilya V. Taydakov, Natalia V. Gogoleva, Alexey A. Sidorov and Igor L. Eremenko
Materials 2020, 13(24), 5689; https://doi.org/10.3390/ma13245689 - 13 Dec 2020
Cited by 22 | Viewed by 3108
Abstract
Varying the temperature of the reaction of [{Cd(pfb)(H2O)4}+n·n(pfb)−], [Ln2(pfb)6(H2O)8]·H2O (Hpfb = pentafluorobenzoic acid), and 1,10-phenanthroline (phen) in MeCN followed by crystallization resulted [...] Read more.
Varying the temperature of the reaction of [{Cd(pfb)(H2O)4}+n·n(pfb)−], [Ln2(pfb)6(H2O)8]·H2O (Hpfb = pentafluorobenzoic acid), and 1,10-phenanthroline (phen) in MeCN followed by crystallization resulted in the isolation of two type of products: 1D-polymers [LnCd(pfb)5(phen)]n·1.5nMeCN (Ln = Eu (I), Gd (II), Tb (III), Dy (IV)) which were isolated at 25 °C, and molecular compounds [Tb2Cd2(pfb)10(phen)2] (V) formed at 75 °C. The transition from a molecular to a polymer structure becomes possible because of intra- and intermolecular interactions between the aromatic cycles of phen and pfb from neighboring tetranuclear Ln2Cd2 fragments. Replacement of cadmium with zinc in the reaction resulted in molecular compounds Ln2Zn2 [Ln2Zn2(pfb)10(phen)2]·4MeCN (Ln = Eu (VI), Tb (VIII), Dy (IX)) and [Gd2Zn2(pfb)10(H2O)2(phen)2]·4MeCN (VII). A new molecular EuCd complex [Eu2Cd2(pfb)10(phen)4]·4MeCN (X)] was isolated from a mixture of cadmium, zinc, and europium pentafluorobenzoates (Cd:Zn:Ln = 1:1:2). Complexes II-IV, VII and IX exhibit magnetic relaxation at liquid helium temperatures in nonzero magnetic fields. Luminescent studies revealed a bright luminescence of complexes with europium(III) and terbium(III) ions. Full article
(This article belongs to the Special Issue Coordination Polymers: Synthesis, Crystal Structure and Multifunctional Applications)
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16 pages, 5027 KiB  
Article
Transition Metal Coordination Polymers with Trans-1,4-Cyclohexanedicarboxylate: Acidity-Controlled Synthesis, Structures and Properties
by Pavel A. Demakov, Artem S. Bogomyakov, Artem S. Urlukov, Aleksandra Yu. Andreeva, Denis G. Samsonenko, Danil N. Dybtsev and Vladimir P. Fedin
Materials 2020, 13(2), 486; https://doi.org/10.3390/ma13020486 - 19 Jan 2020
Cited by 8 | Viewed by 2969
Abstract
Five trans-1,4-cyclohexanedicarboxylate (chdc2−) metal–organic frameworks of transition metals were synthesized in aqueous systems. A careful control of pH, reaction temperature and solvent composition were shown to direct the crystallization of a particular compound. Isostructural [Co(H2O)4(chdc)]n ( [...] Read more.
Five trans-1,4-cyclohexanedicarboxylate (chdc2−) metal–organic frameworks of transition metals were synthesized in aqueous systems. A careful control of pH, reaction temperature and solvent composition were shown to direct the crystallization of a particular compound. Isostructural [Co(H2O)4(chdc)]n (1) and [Fe(H2O)4(chdc)]n (2) consist of one-dimensional hydrogen-bonded chains. Compounds [Cd(H2O)(chdc)]n∙0.5nCH3CN (3), [Mn4(H2O)3(chdc)4]n (4) and [Mn2(Hchdc)2(chdc)]n (5) possess three-dimensional framework structures. The compounds 1, 4 and 5 were further characterized by magnetochemical analysis, which reveals paramagnetic nature of these compounds. A presence of antiferromagnetic exchange at low temperatures is observed for 5 while the antiferromagnetic coupling in 4 is rather strong, even at ambient conditions. The thermal decompositions of 1, 4 and 5 were investigated and the obtained metal oxide (cubic Co3O4 and MnO) samples were analyzed by X-ray diffraction and scanning electron microscopy. Full article
(This article belongs to the Special Issue Coordination Polymers: Synthesis, Crystal Structure and Multifunctional Applications)
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Review

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67 pages, 71724 KiB  
Review
Coordination Polymers Based on Highly Emissive Ligands: Synthesis and Functional Properties
by Anastasia Kuznetsova, Vladislava Matveevskaya, Dmitry Pavlov, Andrei Yakunenkov and Andrei Potapov
Materials 2020, 13(12), 2699; https://doi.org/10.3390/ma13122699 - 13 Jun 2020
Cited by 71 | Viewed by 6668
Abstract
Coordination polymers are constructed from metal ions and bridging ligands, linking them into solid-state structures extending in one (1D), two (2D) or three dimensions (3D). Two- and three-dimensional coordination polymers with potential voids are often referred to as metal-organic frameworks (MOFs) or porous [...] Read more.
Coordination polymers are constructed from metal ions and bridging ligands, linking them into solid-state structures extending in one (1D), two (2D) or three dimensions (3D). Two- and three-dimensional coordination polymers with potential voids are often referred to as metal-organic frameworks (MOFs) or porous coordination polymers. Luminescence is an important property of coordination polymers, often playing a key role in their applications. Photophysical properties of the coordination polymers can be associated with intraligand, metal-centered, guest-centered, metal-to-ligand and ligand-to-metal electron transitions. In recent years, a rapid growth of publications devoted to luminescent or fluorescent coordination polymers can be observed. In this review the use of fluorescent ligands, namely, 4,4′-stilbenedicarboxylic acid, 1,3,4-oxadiazole, thiazole, 2,1,3-benzothiadiazole, terpyridine and carbazole derivatives, naphthalene diimides, 4,4′,4′′-nitrilotribenzoic acid, ruthenium(II) and iridium(III) complexes, boron-dipyrromethene (BODIPY) derivatives, porphyrins, for the construction of coordination polymers are surveyed. Applications of such coordination polymers based on their photophysical properties will be discussed. The review covers the literature published before April 2020. Full article
(This article belongs to the Special Issue Coordination Polymers: Synthesis, Crystal Structure and Multifunctional Applications)
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