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Polymers
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Coordination Polymers: Properties and Applications II
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Coordination Polymers: Properties and Applications II

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Chemistry".

Deadline for manuscript submissions: closed (31 May 2023) | Viewed by 15049

Special Issue Editor

Dr. Chen-I Yang

E-Mail Website
Guest Editor
Department of Chemistry, Tunghai University, Taichung, Taiwan
Interests: coordination polymers; metal–organic frameworks; molecule-based magnets; magnetochemistry
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

This Special Issue is dedicated to the properties and applications of coordination polymers. Coordination polymers, which are crystalline hybrid materials containing inorganic and organic components and possessing extended structures with coordination bonds, have become very attractive in studies of condensed matter. Because of their hybrid characteristics, these materials benefit from having the characteristics of both inorganic and organic building blocks. Consequently, due to this inorganic–organic combination, they frequently possess new and interesting properties or functionalities, such as in electronics, magnetism, host–guest chemistry, ion exchange, catalysis, nanotechnology, fluorescence, nonlinear optics, etc. Therefore, there is a need to explore strategies for designing novel coordination polymers with intriguing network topologies and understanding their structure–property relationships for application.

The objective of this Special Issue is to present original research and reviews focused on the synthesis, characterization, structural topologies, properties, and applications of new type of coordination polymers.

Dr. Chen-I Yang
Guest Editor

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Keywords

  • synthesis and characterization of coordination polymers
  • structural topologies of coordination polymers
  • magnetism
  • host–guest chemistry
  • ion exchange
  • fluorescence
  • catalysis
  • structure–property relationships of coordination polymers

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Published Papers (7 papers)

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Research

11 pages, 4777 KiB  
Article
Cd(II)/Mn(II)/Co(II)/Ni(II)/Zn(II) Coordination Polymers Built from Dicarboxylic Acid/Tetracarboxylic Acid Ligands: Their Structural Diversity and Fluorescence Properties
by Lu Liu, Jian-Min Li, Meng-Di Zhang, Hui-Jie Wang, Ying Li, Zhen-Bei Zhang, Zi-Fang Zhao, Yu Xi, Yuan-Yuan Huang, Jie Xu, Bo Zhang, Jun Chen and Cheng-Xing Cui
Polymers 2023, 15(7), 1803; https://doi.org/10.3390/polym15071803 - 6 Apr 2023
Cited by 1 | Viewed by 1596
Abstract
Six Cd(II)/Mn(II)/Co(II)/Ni(II)/Zn(II) coordination complexes are formulated as [Cd2(X2−)2(μ3-O)2/3]n (1), [Mn2(X2−)2(μ3-O)2/3]n (2), {[Co1.5(Y4− [...] Read more.
Six Cd(II)/Mn(II)/Co(II)/Ni(II)/Zn(II) coordination complexes are formulated as [Cd2(X2−)2(μ3-O)2/3]n (1), [Mn2(X2−)2(μ3-O)2/3]n (2), {[Co1.5(Y4−)0.5(4,4′-bpy)1.5(OH−)]·2H2O}n (3), {[Ni(X2−)(4,4′-bpy)(H2O)2]·4H2O}n (4), [Zn(m-bdc2−)(bebiyh)]n (5), and [Cd(5-tbia2−)(bebiyh)]n (6) (H2X = 3,3′-(2,3,5,6-tetramethyl-1,4-phenylene) dipropionic acid. H4Y = 2,2′-(2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene) dimalonic acid, bebiyh = 1,6-bis(2-ethyl-1H-benzo[d]imidazol-1-yl)hexane, m-H2bdc = 1,3-benzenedicarboxylic acid, and 5-H2tbia = 5-(tert-butyl)isophthalic acid) were obtained by hydrothermal reactions and structurally characterized. Complexes 1 and 2 have a 6-connected 3D architecture and with several point symbols of (36·46·53). Complex 3 features a 5-connected 3D net structure with a point symbol of (5·69). Complex 4 possesses a 4-connected 2D net with a vertex symbol of (44·62). Complex 5 is a 3-connected 2D network with a point symbol of (63). Complex 6 is a (3,3)-connected 2D network with a point symbol of (63)2. In addition, complexes 1 and 4 present good photoluminescence behaviors. The electronic structures of 1 and 4 were investigated with the density functional theory (DFT) method to understand the photoluminescence behaviors. Full article
(This article belongs to the Special Issue Coordination Polymers: Properties and Applications II)
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19 pages, 32127 KiB  
Article
New Self-Healing Metallosupramolecular Copolymers with a Complex of Cobalt Acrylate and 4′-Phenyl-2,2′:6′,2″-terpyridine
by Evgeny S. Sorin, Rose K. Baimuratova, Igor E. Uflyand, Evgeniya O. Perepelitsina, Denis V. Anokhin, Dmitry A. Ivanov and Gulzhian I. Dzhardimalieva
Polymers 2023, 15(6), 1472; https://doi.org/10.3390/polym15061472 - 16 Mar 2023
Cited by 2 | Viewed by 2217
Abstract
Currently, the chemistry of self-healing polymers is aimed not only at obtaining materials with high self-healing efficiency, but also at improving their mechanical performance. This paper reports on a successful attempt to obtain self-healing copolymers films of acrylic acid, acrylamide and a new [...] Read more.
Currently, the chemistry of self-healing polymers is aimed not only at obtaining materials with high self-healing efficiency, but also at improving their mechanical performance. This paper reports on a successful attempt to obtain self-healing copolymers films of acrylic acid, acrylamide and a new metal-containing complex of cobalt acrylate with a 4′-phenyl-2,2′:6′,2″-terpyridine ligand. Samples of the formed copolymer films were characterized by ATR/FT-IR and UV-vis spectroscopy, elemental analysis, DSC and TGA, SAXS, WAXS and XRD studies. The incorporation of the metal-containing complex directly into the polymer chain results in an excellent tensile strength (122 MPa) and modulus of elasticity (4.3 GPa) of the obtained films. The resulting copolymers demonstrated self-healing properties both at acidic pH (assisted by HCl healing) with effective preservation of mechanical properties, and autonomously in a humid atmosphere at room temperature without the use of initiators. At the same time, with a decrease in the content of acrylamide, a decrease in the reducing properties was observed, possibly due to an insufficient amount of amide groups to form hydrogen bonds through the interface with terminal carboxyl groups, as well as a decrease in the stability of complexes in samples with a high content of acrylic acid. Full article
(This article belongs to the Special Issue Coordination Polymers: Properties and Applications II)
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20 pages, 5963 KiB  
Article
Synthesis and Design of Hybrid Metalloporphyrin Polymers Based on Palladium (II) and Copper (II) Cations and Axial Complexes of Pyridyl-Substituted Sn(IV)Porphyrins with Octopamine
by Anastasia E. Likhonina, Galina M. Mamardashvili, Ilya A. Khodov and Nugzar Z. Mamardashvili
Polymers 2023, 15(4), 1055; https://doi.org/10.3390/polym15041055 - 20 Feb 2023
Cited by 2 | Viewed by 2335
Abstract
Supramolecular metalloporphyrin polymers formed by binding tetrapyrrolic macrocycle peripheral nitrogen atoms to Pd(II) cations and Sn(IV)porphyrins extra-ligands reaction centers to Cu(II) cations were obtained and identified. The structure and the formation mechanism of obtained hydrophobic Sn(IV)-porphyrin oligomers and polymers in solution were established, [...] Read more.
Supramolecular metalloporphyrin polymers formed by binding tetrapyrrolic macrocycle peripheral nitrogen atoms to Pd(II) cations and Sn(IV)porphyrins extra-ligands reaction centers to Cu(II) cations were obtained and identified. The structure and the formation mechanism of obtained hydrophobic Sn(IV)-porphyrin oligomers and polymers in solution were established, and their resistance to UV radiation and changes in solution temperature was studied. It was shown that the investigated polyporphyrin nanostructures are porous materials with predominance cylindrical mesopores. Density functional theory (DFT) was used to geometrically optimize the experimentally obtained supramolecular porphyrin polymers. The sizes of unit cells in porphyrin tubular structures were determined and coincided with the experimental data. The results obtained can be used to create highly porous materials for separation, storage, transportation, and controlled release of substrates of different nature, including highly volatile, explosive, and toxic gases. Full article
(This article belongs to the Special Issue Coordination Polymers: Properties and Applications II)
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16 pages, 4770 KiB  
Article
Analytical Determination of Cephalosporin Antibiotics Using Coordination Polymer Based on Cobalt Terephthalate as a Sorbent
by Maria A. Chernomorova, Marina S. Myakinina, Vladimir A. Zhinzhilo and Igor E. Uflyand
Polymers 2023, 15(3), 548; https://doi.org/10.3390/polym15030548 - 20 Jan 2023
Cited by 3 | Viewed by 2189
Abstract
In this work, a coordination polymer based on cobalt terephthalate was obtained and characterized by elemental analysis, infrared spectroscopy, X-ray diffraction analysis, and scanning electron microscopy. The coordination polymer was tested as a sorbent for the solid-phase extraction of cephalosporin antibiotics, including ceftriaxone, [...] Read more.
In this work, a coordination polymer based on cobalt terephthalate was obtained and characterized by elemental analysis, infrared spectroscopy, X-ray diffraction analysis, and scanning electron microscopy. The coordination polymer was tested as a sorbent for the solid-phase extraction of cephalosporin antibiotics, including ceftriaxone, cefotaxime, and cefazolin, from aqueous solutions. The coordination polymer had a high adsorption capacity (520.0 mg/g). Antibiotics adsorption followed pseudo-second order kinetic model and the Freundlich isotherm model. The calculated thermodynamic parameters indicate a spontaneous process. The resulting coordination polymer has good stability and reusability. The possibility of separating the studied cephalosporins on a chromatographic column filled with a coordination polymer was shown. This work opens great prospects for the development and application of a coordination polymer based on cobalt terephthalate for the removal of cephalosporins from ambient water. Full article
(This article belongs to the Special Issue Coordination Polymers: Properties and Applications II)
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15 pages, 5505 KiB  
Article
Microporous Polymelamine Framework Functionalized with Re(I) Tricarbonyl Complexes for CO2 Absorption and Reduction
by Stefania Zappia, Elena Perju, Andrei Bejan, Adina Coroaba, Filippo Bossola, Juqin Zeng, Daniele Sassone, Luminita Marin, Silvia Destri and William Porzio
Polymers 2022, 14(24), 5472; https://doi.org/10.3390/polym14245472 - 14 Dec 2022
Cited by 2 | Viewed by 1936
Abstract
A mixture of polymeric complexes based on the reaction between Re(CO)5Cl and the porous polymeric network coming from the coupling of melamine and benzene-1,3,5-tricarboxaldehyde was obtained and characterized by FTIR, NMR, SEM, XPS, ICP, XRD, and cyclic voltammetry (CV). The formed [...] Read more.
A mixture of polymeric complexes based on the reaction between Re(CO)5Cl and the porous polymeric network coming from the coupling of melamine and benzene-1,3,5-tricarboxaldehyde was obtained and characterized by FTIR, NMR, SEM, XPS, ICP, XRD, and cyclic voltammetry (CV). The formed rhenium-based porous hybrid material reveals a noticeable capability of CO2 absorption. The gas absorption amount measured at 295 K was close to 44 cm3/g at 1 atm. An interesting catalytic activity for CO2 reduction reaction (CO2RR) is observed, resulting in a turn over-number (TON) close to 6.3 under 80 min of test at −1.8 V vs. Ag/AgCl in a TBAPF6 0.1 M ACN solution. A possible use as filler in membranes or columns can be envisaged. Full article
(This article belongs to the Special Issue Coordination Polymers: Properties and Applications II)
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14 pages, 2978 KiB  
Article
New Titanium(IV)-Alkoxide Complexes Bearing Bidentate OO Ligand with the Camphyl Linker as Catalysts for High-Temperature Ethylene Polymerization and Ethylene/1-Octene Copolymerization
by Vladislav A. Tuskaev, Svetlana Ch. Gagieva, Dmitrii A. Kurmaev, Yulia V. Nelyubina, Petr V. Primakov, Maria D. Evseeva, Evgenii K. Golubev, Mikhail I. Buzin, Galina G. Nikiforova, Pavel B. Dzhevakov, Viktor I. Privalov, Kasim F. Magomedov and Boris M. Bulychev
Polymers 2022, 14(21), 4735; https://doi.org/10.3390/polym14214735 - 4 Nov 2022
Cited by 2 | Viewed by 1827
Abstract
In order to increase the thermal stability of olefin polymerization precatalysts, new titanium(IV) complexes with diolate ligands differing in the degree of steric hindrances were synthesized from readily available precursor (±)camphor. The structures of the complexes 1–2 were established by X-ray diffraction. Complexes [...] Read more.
In order to increase the thermal stability of olefin polymerization precatalysts, new titanium(IV) complexes with diolate ligands differing in the degree of steric hindrances were synthesized from readily available precursor (±)camphor. The structures of the complexes 1–2 were established by X-ray diffraction. Complexes 1–4 in the presence of an activator {EtnAlCl3-n + Bu2Mg} catalyzed the synthesis of UHMWPE with an Mv up to 10 million and a productivity of up to 3300 kg/molTi·atm·h. The obtained polymers are obviously characterized by a low density of macromolecular entanglement, which makes it possible to use the solid-phase method for their processing. The mechanical characteristics of the oriented UHMWPE films had a breaking strength up to 2.7 GPa and an elastic modulus of up to 151 GPa. The precatalysts 1–4 were also active in ethylene/1-octene copolymerization. The comonomer content was in the range of 1.4–4.6 mol%. The use of a rigid linker and an increase in the steric load of the diolate complexes ensured the thermal stability of the catalytic system in the range of 50–70 °C. Full article
(This article belongs to the Special Issue Coordination Polymers: Properties and Applications II)
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19 pages, 3486 KiB  
Article
Effect of Activator and Outgoing Ligand Nature on the Catalytic Behavior of Bis(phenoxy-imine) Ti(IV) Complexes in the Polymerization of Ethylene and Its Copolymerization with Higher Olefins
by Svetlana Ch. Gagieva, Kasim F. Magomedov, Vladislav A. Tuskaev, Vyacheslav S. Bogdanov, Dmitrii A. Kurmaev, Evgenii K. Golubev, Gleb L. Denisov, Galina G. Nikiforova, Maria D. Evseeva, Daniele Saracheno, Mikhail I. Buzin, Pavel B. Dzhevakov, Viktor I. Privalov and Boris M. Bulychev
Polymers 2022, 14(20), 4397; https://doi.org/10.3390/polym14204397 - 18 Oct 2022
Cited by 6 | Viewed by 2164
Abstract
A series of bis(phenoxy-imine) (FI) titanium(IV) and zirconium(IV) complexes have been synthesized. The effect of the nature of the activator (MAO, combinations EtnAlCl3-n + Bu2Mg and iBu3Al + [Ph3C]+[B(C6F5 [...] Read more.
A series of bis(phenoxy-imine) (FI) titanium(IV) and zirconium(IV) complexes have been synthesized. The effect of the nature of the activator (MAO, combinations EtnAlCl3-n + Bu2Mg and iBu3Al + [Ph3C]+[B(C6F5)4]−) on the catalytic activity and properties of the resulting polymers was studied. It was found that Ti-Fi complexes, despite the nature of the outgoing ligands (Cl or iPrO) in the presence of Al/Mg activators, effectively catalyze the polymerization of ethylene (with the formation of UHMWPE); copolymerization of ethylene with 1-octene (with the formation of ultra-high molecular weight copolymers); and the ternary copolymerization of ethylene, propylene and 5-vinyl-2-norbornene (with the formation of polyolefin elastomers). It has been shown that Zr-FI complexes are not activated by these Al/Mg compositions. The resulting UHMWPE can be processed by a solventless method into high-strength and high-modulus oriented films; however, their mechanical characteristics do not exceed those obtained using MAO. Full article
(This article belongs to the Special Issue Coordination Polymers: Properties and Applications II)
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