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Advanced Coordination Polymers

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

Deadline for manuscript submissions: closed (20 January 2022) | Viewed by 34877

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Guest Editor
Crystallography and Coordination Chemistry of Materials Group, Institute of Nanoscience and Nanotechnology, NCSR “Demokritos”, Patriarchou Grigoriou & Neapoleos 27, 153 10 Agia Paraskevi, Attiki, Greece
Interests: coordination chemistry; molecular magnetic materials; molecular materials; structure–property correlations; single-crystal X-ray crystallography

Special Issue Information

Dear Colleagues,

The field of coordination polymers has been growing during the last decades, because of the enormous variety of interesting molecular topologies they present, often unprecedented in inorganic compounds and in minerals, and of their excellent properties with promising applications in gas storage, gas/vapor separation, size-, shape-, and enantio-selective catalysis, luminescent and fluorescent materials, and drug storage and delivery. The framework topologies are primarily dependent upon the structural features of the building block units, i.e., the coordination preferences of the metals and/or metal clusters serving as nodes and the functionality of the organic ligands serving as spacers. The chemical and structural diversity of coordination polymers is also dependent upon various chemical factors, such as temperature, pH, reaction solvent, template effects, role of the counteranion as a coordinating or not-coordinating building-block, etc.

This Special Issue aims to collect high-quality full articles containing original research results describing the latest advances in the synthesis, structural characterization, topologies, properties, and applications of all types of coordination polymers.

Dr. Catherine P. Raptopoulou
Guest Editor

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Keywords

  • coordination polymers
  • synthesis, structures, and topology of coordination polymers
  • porous materials
  • applications of coordination polymers in energy
  • applications of coordination polymers in catalysis
  • applications of coordination polymers in gas/vapor separation
  • multifunctional materials
  • magnetic coordination polymers

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Published Papers (5 papers)

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Research

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24 pages, 3966 KiB  
Article
From 1D Coordination Polymers to Metal Organic Frameworks by the Use of 2-Pyridyl Oximes
by Ioannis Mylonas-Margaritis, Auban Gérard, Katerina Skordi, Julia Mayans, Anastasios Tasiopoulos, Patrick McArdle and Constantina Papatriantafyllopoulou
Materials 2020, 13(18), 4084; https://doi.org/10.3390/ma13184084 - 14 Sep 2020
Cited by 9 | Viewed by 3224
Abstract
The synthesis and characterization of coordination polymers and metal–organic frameworks (MOFs) has attracted a significant interest over the last decades due to their fascinating physical properties, as well as their use in a wide range of technological, environmental, and biomedical applications. The initial [...] Read more.
The synthesis and characterization of coordination polymers and metal–organic frameworks (MOFs) has attracted a significant interest over the last decades due to their fascinating physical properties, as well as their use in a wide range of technological, environmental, and biomedical applications. The initial use of 2-pyridyl oximic ligands such as pyridine-2 amidoxime (H2pyaox) and 2-methyl pyridyl ketoxime (Hmpko) in combination with 1,2,4,5-benzene tetracarboxylic acid (pyromellitic acid), H4pma, provided access to nine new compounds whose structures and properties are discussed in detail. Among them, [Zn2(pma)(H2pyaox)2(H2O)2]n (3) and [Cu4(OH)2(pma)(mpko)2]n (9) are the first MOFs based on a 2-pyridyl oxime with 9 possessing a novel 3,4,5,8-c net topology. [Zn2(pma)(H2pyaox)2]n (2), [Cu2(pma)(H2pyaox)2(DMF)2]n (6), and [Cu2(pma)(Hmpko)2(DMF)2]n (8) join a small family of coordination polymers containing an oximic ligand. 9 exhibits selectivity for FeIII ions adsorption, as was demonstrated by a variety of techniques including UV-vis, EDX, and magnetism. DC magnetic susceptibility studies in 9 revealed the presence of strong antiferromagnetic interactions between the metal centers, which lead to a diamagnetic ground state; it was also found that the magnetic properties of 9 are affected by the amount of the encapsulated Fe3+ ions, which is a very desirable property for the development of magnetism-based sensors. Full article
(This article belongs to the Special Issue Advanced Coordination Polymers)
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14 pages, 2016 KiB  
Article
‘Metal Complexes as Ligands’ for the Synthesis of Coordination Polymers: A MnIII Monomer as a Building Block for the Preparation of an Unprecedented 1-D {MnIIMnIII}n Linear Chain
by Konstantinos N. Pantelis, Georgios Karotsis, Christos Lampropoulos, Luís Cunha-Silva, Albert Escuer and Theocharis C. Stamatatos
Materials 2020, 13(6), 1352; https://doi.org/10.3390/ma13061352 - 17 Mar 2020
Cited by 3 | Viewed by 3366
Abstract
A relatively unexplored synthetic route in redox-active Mn(II/III) coordination chemistry has been employed toward the preparation of a new mixed-valence MnII/III 1-D linear chain from the reaction of [MnIII(sacb)2] precursor with a MnII source, where sacbH [...] Read more.
A relatively unexplored synthetic route in redox-active Mn(II/III) coordination chemistry has been employed toward the preparation of a new mixed-valence MnII/III 1-D linear chain from the reaction of [MnIII(sacb)2] precursor with a MnII source, where sacbH2 is the Schiff base ligand N-salicylidene-2-amino-5-chlorobenzoic acid. The mononuclear (Pr2NH2)[MnIII(sacb)2] (1) compound was obtained in excellent yields (>85%) from the 1:2:3 reaction of Mn(O2CMe)2∙4H2O, sacbH2 and Pr2NH, respectively. In 1, the two doubly deprotonated sacb2− ligands act as Ocarboxylate,Nimine,Ophenoxide-tridentate chelates, while the second carboxylate O atom of sacb2− is dangling and H-bonded to the Pr2NH2+ countercation. Complex 1 was subsequently used as a ‘ligand’ to react stoichiometrically with the ‘metal’ Mn(NO3)2∙4H2O, thus leading to the 1-D coordination polymer {[MnIIMnIII(sacb)2(H2O)2(MeOH)2](NO3)}n (2) in good yields (~50%). The removal of Pr2NH2+ from the vicinity of the [MnIII(sacb)2] metalloligand has rendered possible (vide infra) the coordination of the second Ocarboxylate of sacb2− to neighboring {MnII(H2O)2(MeOH)2}2+ units, and consequently the formation of the 1-D polymer 2. Direct-current (dc) magnetic susceptibility studies revealed the presence of very weak antiferromagnetic exchange interactions between alternating MnIII and MnII atoms with a coupling constant of J = −0.08 cm−1 for g = 2.00. The combined results demonstrate the potential of the ‘metal complexes as ligands’ approach to yield new mixed-valence Mn(II/III) coordination polymers with interesting structural motifs and physicochemical properties. Full article
(This article belongs to the Special Issue Advanced Coordination Polymers)
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Review

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32 pages, 3534 KiB  
Review
Metal-Organic Frameworks: Synthetic Methods and Potential Applications
by Catherine P. Raptopoulou
Materials 2021, 14(2), 310; https://doi.org/10.3390/ma14020310 - 9 Jan 2021
Cited by 172 | Viewed by 17420
Abstract
Metal-organic frameworks represent a porous class of materials that are build up from metal ions or oligonuclear metallic complexes and organic ligands. They can be considered as sub-class of coordination polymers and can be extended into one-dimension, two-dimensions, and three-dimensions. Depending on the [...] Read more.
Metal-organic frameworks represent a porous class of materials that are build up from metal ions or oligonuclear metallic complexes and organic ligands. They can be considered as sub-class of coordination polymers and can be extended into one-dimension, two-dimensions, and three-dimensions. Depending on the size of the pores, MOFs are divided into nanoporous, mesoporous, and macroporous items. The latter two are usually amorphous. MOFs display high porosity, a large specific surface area, and high thermal stability due to the presence of coordination bonds. The pores can incorporate neutral molecules, such as solvent molecules, anions, and cations, depending on the overall charge of the MOF, gas molecules, and biomolecules. The structural diversity of the framework and the multifunctionality of the pores render this class of materials as candidates for a plethora of environmental and biomedical applications and also as catalysts, sensors, piezo/ferroelectric, thermoelectric, and magnetic materials. In the present review, the synthetic methods reported in the literature for preparing MOFs and their derived materials, and their potential applications in environment, energy, and biomedicine are discussed. Full article
(This article belongs to the Special Issue Advanced Coordination Polymers)
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16 pages, 3906 KiB  
Review
Cyclodextrins Modified/Coated Metal–Organic Frameworks
by Huacheng Zhang, Zhaona Liu and Jian Shen
Materials 2020, 13(6), 1273; https://doi.org/10.3390/ma13061273 - 11 Mar 2020
Cited by 25 | Viewed by 4157
Abstract
Recent progress about a novel organic–inorganic hybrid materials, namely cyclodextrins (CDs) modified/coated metal–organic frameworks (MOFs) is summarized by using a special categorization method focusing on the interactions between CDs and MOFs moieties, such as ligand–metal cations interactions, supramolecular interactions including host–guest interactions and [...] Read more.
Recent progress about a novel organic–inorganic hybrid materials, namely cyclodextrins (CDs) modified/coated metal–organic frameworks (MOFs) is summarized by using a special categorization method focusing on the interactions between CDs and MOFs moieties, such as ligand–metal cations interactions, supramolecular interactions including host–guest interactions and hydrogen bonding, as well as covalent bonds. This review mainly focuses on the interactions between CDs and MOFs and the strategy of combining them together, diverse external stimuli responsiveness of CDs-modified/coated MOFs, as well as applications of these hybrid materials to drug delivery and release system, catalysis and detection materials. Additionally, due to the importance of investigating advanced chemical architectures and physiochemical properties of CDs-modified/coated MOFs, a separate section is involved in diverse characterization methods and instruments. Furthermore, this minireview also foresees future research directions in this rapidly developing field. Full article
(This article belongs to the Special Issue Advanced Coordination Polymers)
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Other

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10 pages, 1221 KiB  
Perspective
Metal-Organic Frameworks (MOFs)-Based Nanomaterials for Drug Delivery
by Mohammad Reza Saeb, Navid Rabiee, Masoud Mozafari and Ebrahim Mostafavi
Materials 2021, 14(13), 3652; https://doi.org/10.3390/ma14133652 - 30 Jun 2021
Cited by 66 | Viewed by 5883
Abstract
The composition and topology of metal-organic frameworks (MOFs) are exceptionally tailorable; moreover, they are extremely porous and represent an excellent Brunauer–Emmett–Teller (BET) surface area (≈3000–6000 m2·g−1). Nanoscale MOFs (NMOFs), as cargo nanocarriers, have increasingly attracted the attention of scientists [...] Read more.
The composition and topology of metal-organic frameworks (MOFs) are exceptionally tailorable; moreover, they are extremely porous and represent an excellent Brunauer–Emmett–Teller (BET) surface area (≈3000–6000 m2·g−1). Nanoscale MOFs (NMOFs), as cargo nanocarriers, have increasingly attracted the attention of scientists and biotechnologists during the past decade, in parallel with the evolution in the use of porous nanomaterials in biomedicine. Compared to other nanoparticle-based delivery systems, such as porous nanosilica, nanomicelles, and dendrimer-encapsulated nanoparticles, NMOFs are more flexible, have a higher biodegradability potential, and can be more easily functionalized to meet the required level of host–guest interactions, while preserving a larger and fully adjustable pore window in most cases. Due to these unique properties, NMOFs have the potential to carry anticancer cargos. In contrast to almost all porous materials, MOFs can be synthesized in diverse morphologies, including spherical, ellipsoidal, cubic, hexagonal, and octahedral, which facilitates the acceptance of various drugs and genes. Full article
(This article belongs to the Special Issue Advanced Coordination Polymers)
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