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Crystals
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Coordination Polymers
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Coordination Polymers

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

Deadline for manuscript submissions: closed (31 May 2021) | Viewed by 18776

Special Issue Editors

Assist. Prof. Boris-Marko Kukovec

E-Mail Website
Guest Editor
Department of Physical Chemistry, Faculty of Chemistry and Technology, University of Split, Ruđera Boškovića 35, HR-21000 Split, Croatia
Interests: coordination chemistry; chemical crystallography; coordination polymers; crystal engineering; polymorphism; hydrogen bonding
Assoc. Prof. Marijana Đaković

E-Mail Website
Guest Editor
Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, HR-10000 Zagreb, Croatia
Interests: crystal engineering; chemical crystallography; hydrogen and halogen bonds; coordination polymers; flexible crystalline materials

Special Issue Information

Dear Colleagues,

Coordination polymers (CPs), the infinite systems assembled from metal ions and organic ligands as the main building units and linked together by covalent bonds, are extensively studied in supramolecular chemistry and materials chemistry due to their structural diversity and various applications, e.g., as porous materials, in catalysis, ion exchange, sorption, in purification, separation, and storage of gases, including many interesting properties such as conductivity, non-linear optical, luminescent, magnetic, and mechanical properties.

Coordination polymers containing d-block transition metals have attracted attention mainly due to the many different oxidation states they present and various, but mostly predictable, coordination environments they deliver. In contrast, involvement of the lanthanide ions in building coordination polymers typically results in highly unpredictable coordination polyhedra with high coordination numbers.  

Porous coordination polymers form a class of CPs that have gained extensive attention due to the possible gas and solvent sorption/desorption. The solvent sorption can lead to color change (solvatochromism) because of the change in the coordination environment of the metal. Some porous coordination polymers can be reversibly hydrated, leading to the amorphous phase upon desolvation and again to the crystal phase upon solvation. The vapor sorption/desorption may also lead to single-crystal-to-single-crystal phase transformations, an important phenomenon in solid-state chemistry, enabling the structure determination of the transformed structure as well and deciphering the transformation mechanism.

 We invite contributions on the synthesis of the coordination polymers (classical, solvothermal, mechanochemical) and characterization by various methods (SCXRD, PXRD, spectroscopic and thermal methods). While contributions reporting their properties (magnetic, luminescent, mechanical, etc.) and possible applications are encouraged, studies reporting coordination polymers because of their intriguing aesthetics are also welcome. We particularly encourage topological studies, gas and solvent sorption/desorption studies, including single-crystal-to-single-crystal phase transformations and solvatochromism. 

Assist. Prof. Boris-Marko Kukovec
Assoc. Prof. Marijana Đaković
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 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. 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 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

  • Hydrothermal synthesis
  • Mechanochemical synthesis
  • Magnetism
  • Luminescence
  • Catalysis
  • Mechanical properties
  • Gas and solvent sorption/desorption
  • Solvatochromism
  • Single-crystal-to-single-crystal phase transformation
  • Topology

Published Papers (8 papers)

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Research

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7 pages, 1342 KiB  
Article
Synthesis and Structures of TiIII and TiIV Complexes Supported by a Bulky Guanidinate Ligand
by Awal Noor
Crystals 2021, 11(8), 886; https://doi.org/10.3390/cryst11080886 - 29 Jul 2021
Viewed by 1678
Abstract
In this work, titanium complexes of the bidentate bulky guanidine ligand [{(Dip)N}2CNR2]H (where Dip = C6H3iPr2-2,6 and R = CH(CH3)2) (LH) were prepared. Reaction of LH with one equivalent [...] Read more.
In this work, titanium complexes of the bidentate bulky guanidine ligand [{(Dip)N}2CNR2]H (where Dip = C6H3iPr2-2,6 and R = CH(CH3)2) (LH) were prepared. Reaction of LH with one equivalent of [(CH3)2NTiCl3] underwent amine elimination to afford the monomeric complex [LTiCl3] (1) in high yield. Attempts to reduce 1 with potassium graphite (KC8) in tetrahydrofuran (THF) were unsuccessful. However, reacting 1 with 3.3 equivalents of KC8 in hexane led to the first example of structurally characterized mono-guanidinate ligand stabilized dimeric TiIII complex [LTiCl(μ–Cl)]2 (2). The synthesized complexes were characterized by NMR spectroscopy and the structures were further confirmed by X-ray crystallography. Full article
(This article belongs to the Special Issue Coordination Polymers)
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13 pages, 3586 KiB  
Article
The Preparation, Morphological Characterization and Possible Electroanalytical Application of a Hydroxyapatite-Modified Glassy Carbon Electrode
by Ivana Škugor Rončević, Marijo Buzuk, Maša Buljac and Nives Vladislavić
Crystals 2021, 11(7), 772; https://doi.org/10.3390/cryst11070772 - 01 Jul 2021
Cited by 1 | Viewed by 1915
Abstract
By simple modification of a GC electrode with biofunctional material, hydroxyapatite (HAp), an efficient electroanalytical tool, was designed and constructed. Modification of the GC surface includes two steps in synthesis: electrochemical deposition and chemical conversion. The properties, structure, and morphology of a nanosized [...] Read more.
By simple modification of a GC electrode with biofunctional material, hydroxyapatite (HAp), an efficient electroanalytical tool, was designed and constructed. Modification of the GC surface includes two steps in synthesis: electrochemical deposition and chemical conversion. The properties, structure, and morphology of a nanosized material formed on a surface and absorbability were studied by electrochemical impedance spectroscopy, Fourier-transform infrared spectroscopy and scanning electron microscopy with energy-dispersive spectroscopy analysis. Numerous methods in this work confirmed that the developed method for controlled HAp deposition results in a HAp open structure and uniform morphology, which is capable of the selective absorption of the target species. The main goal of this study was the possibility of using a HAp-modified electrode for the fast screening of copper, cadmium, and lead content in honey and sugar samples. The electrochemical behavior and potential of the electroanalytical determination of heavy metals using the HAp/GC electrode were studied using cyclic voltammetry and square wave anodic stripping voltammetry. The HAp/GC electrode exhibited great performance in the determination of heavy metals, based on the reduction of target metals, because of the high absorbability of the HAp film and the electroanalytical properties of GC. A linear response between 10 and 1000 μg/L for Cu and Pb and 1 and 100 μg/L for Cd, with an estimated detection limit of 2.0, 10.0, and 0.9 μg/L, respectively, was obtained. Full article
(This article belongs to the Special Issue Coordination Polymers)
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15 pages, 3981 KiB  
Article
Structural Evolution in the RE(OAc)3 · 2AcOH Structure Type. A Non-Linear, One-Dimensional Coordination Polymer with Unequal Interatomic Rare Earth Distances
by Markus Haase, Philipp Rissiek, Marianne Gather-Steckhan, Felix Henkel and Hans Reuter
Crystals 2021, 11(7), 768; https://doi.org/10.3390/cryst11070768 - 30 Jun 2021
Cited by 1 | Viewed by 1624
Abstract
The existing range of the centrosymmetric, triclinic RE(OAc)3 · 2AcOH structure type has been extended for RE = Eu and Gd while the structure data of the Nd- and Sm-compounds have been revised and corrected, respectively, using low temperature (T = 100 [...] Read more.
The existing range of the centrosymmetric, triclinic RE(OAc)3 · 2AcOH structure type has been extended for RE = Eu and Gd while the structure data of the Nd- and Sm-compounds have been revised and corrected, respectively, using low temperature (T = 100 K), well resolved (2θmax = 56°), highly redundant SCXRD data in order to evaluate the structural evolution within this class of acetic acid solvates by statistical methods. Within the nine-fold mono-capped square-antiprismatic coordination spheres of the RE3+ ions, RE-O distances decrease as a result of lanthanide contraction; some with different rates depending on the coordination modes (2.11/2.21) of the acetate ions. The experimental data show that the internal structural parameters of the acetate ions also correlate with their coordination modes. Both acetic acid molecules act as hydrogen bond donors but only one as monodentate ligand. The geometries of the hydrogen bonds reveal that they are strongly influenced by the size of the rare earth atom. The non-linear, one-dimensional coordination polymer propagates with unequal RE···RE distances along the a-axis. Rods of the coordination polymer are arranged in layers congruently stacked above each other with the hydrogen bonded acetic acid molecules as filler in between. In most cases, data fitting is best described in terms of a quadratic rather than a linear regression analysis. Full article
(This article belongs to the Special Issue Coordination Polymers)
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11 pages, 3087 KiB  
Article
Chalcogen S∙∙∙S Bonding in Supramolecular Assemblies of Cadmium(II) Coordination Polymers with Pyridine-Based Ligands
by Nives Matijaković Mlinarić, Nikolina Penić, Boris-Marko Kukovec and Marijana Đaković
Crystals 2021, 11(6), 697; https://doi.org/10.3390/cryst11060697 - 18 Jun 2021
Cited by 1 | Viewed by 1939
Abstract
Two cadmium(II) coordination polymers, with thiocyanate and pyridine-based ligands e.g., 3-acetamidopyridine (3-Acpy) and niazid (nicotinic acid hydrazide, nia), namely one-dimensional {[Cd(SCN)2(3-Acpy)]}n (1) and two-dimensional {[Cd(SCN)2(nia)]}n (2), are prepared in the mixture of water [...] Read more.
Two cadmium(II) coordination polymers, with thiocyanate and pyridine-based ligands e.g., 3-acetamidopyridine (3-Acpy) and niazid (nicotinic acid hydrazide, nia), namely one-dimensional {[Cd(SCN)2(3-Acpy)]}n (1) and two-dimensional {[Cd(SCN)2(nia)]}n (2), are prepared in the mixture of water and ethanol. The adjacent cadmium(II) ions in 1 are bridged by two N,S-thiocyanate ions and an N,O-bridging 3-Acpy molecule, forming infinite one-dimensional polymeric chains, which are assembled by the intermolecular N–H∙∙∙S hydrogen bonds in one direction and by the intermolecular S∙∙∙S chalcogen bonds in another direction. Within the coordination network of 2, the adjacent cadmium(II) ions are bridged by N,S-thiocyanate ions in one direction and by N,O,N’-chelating and bridging nia molecules in another direction. The coordination networks of 2 are assembled by the intermolecular N–H∙∙∙S and N–H∙∙∙N hydrogen bonds and S∙∙∙S chalcogen bonds. Being the only supramolecular interactions responsible for assembling the polymer chains of 1 in the particular direction, the chalcogen S∙∙∙S bonds are more significant in the structure of 1, whilst the chalcogen S∙∙∙S bonds which act in cooperation with the N–H∙∙∙S and N–H∙∙∙N hydrogen bonds are of less significance in the structure of 2. Full article
(This article belongs to the Special Issue Coordination Polymers)
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17 pages, 5889 KiB  
Article
Rapid Microwave Method for Synthesis of Iron Oxide Particles under Specific Conditions
by Ivana Mitar, Lucija Guć, Željka Soldin, Martina Vrankić, Andrea Paut, Ante Prkić and Stjepko Krehula
Crystals 2021, 11(4), 383; https://doi.org/10.3390/cryst11040383 - 06 Apr 2021
Cited by 11 | Viewed by 2595
Abstract
The advantages of microwave technology over conventionally conducted experiments are numerous. Some of them are reduction in reaction time, a higher degree of process control, repeatability, and work safety. Microwave synthesis routes require a complete description of the experimental details, instrumentation, and design [...] Read more.
The advantages of microwave technology over conventionally conducted experiments are numerous. Some of them are reduction in reaction time, a higher degree of process control, repeatability, and work safety. Microwave synthesis routes require a complete description of the experimental details, instrumentation, and design program of a microwave oven used in the experiments. In this work, microwave-assisted hydrothermal synthesis of hematite (α-Fe2O3) particles from 0.1 M FeCl3 solution in highly alkaline media with heating in a microwave oven at continuous microwave emission of 800 W at 150 °C, 200 °C, and 250 °C for 20 min are presented. Also, the influence of the percentage of the addition of a cationic surfactant, cetyltrimethylammonium bromide (CTAB) on the composition, size, and shape of the final product was investigated. The samples precipitated at 150 °C formed a final product consisting of goethite (α-FeOOH) and hematite particles in contrast to the those precipitated at 200 °C and 250 °C where pure hematite phase was obtained. In these synthesis routes, the CTAB caused to slow down the rate of the goethite-to-hematite transformation process at temperatures at 200 °C but did not affect the transformation at 250 °C. Full article
(This article belongs to the Special Issue Coordination Polymers)
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18 pages, 2618 KiB  
Article
Spin State Behavior of A Spin-Crossover Iron(II) Complex with N,N′-Disubstituted 2,6-bis(pyrazol-3-yl)pyridine: A Combined Study by X-ray Diffraction and NMR Spectroscopy
by Elizaveta K. Melnikova, Dmitry Yu. Aleshin, Igor A. Nikovskiy, Gleb L. Denisov and Yulia V. Nelyubina
Crystals 2020, 10(9), 793; https://doi.org/10.3390/cryst10090793 - 08 Sep 2020
Cited by 13 | Viewed by 2774
Abstract
A series of three different solvatomorphs of a new iron(II) complex with N,N′-disubstituted 2,6-bis(pyrazol-3-yl)pyridine, including those with the same lattice solvent, has been identified by X-ray diffraction under the same crystallization conditions with the metal ion trapped in the different spin states. A [...] Read more.
A series of three different solvatomorphs of a new iron(II) complex with N,N′-disubstituted 2,6-bis(pyrazol-3-yl)pyridine, including those with the same lattice solvent, has been identified by X-ray diffraction under the same crystallization conditions with the metal ion trapped in the different spin states. A thermally induced switching between them, however, occurs in a solution, as unambiguously confirmed by the Evans technique and an analysis of paramagnetic chemical shifts, both based on variable-temperature NMR spectroscopy. The observed stabilization of the high-spin state by an electron-donating substituent contributes to the controversial results for the iron(II) complexes of 2,6-bis(pyrazol-3-yl)pyridines, preventing ‘molecular’ design of their spin-crossover activity; the synthesized complex being only the fourth of the spin-crossover (SCO)-active kind with an N,N′-disubstituted ligand. Full article
(This article belongs to the Special Issue Coordination Polymers)
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13 pages, 2325 KiB  
Article
2D Layer Arrangement of Solely [HS-HS] or [LS-LS] Molecules in the [HS-LS] State of a Dinuclear Fe(II) Spin Crossover Complex
by Fabian Fürmeyer, Luca M. Carrella and Eva Rentschler
Crystals 2020, 10(6), 448; https://doi.org/10.3390/cryst10060448 - 31 May 2020
Cited by 1 | Viewed by 2246
Abstract
Herein we report the synthesis and characterization of three new dinuclear iron(II) complexes [FeII2(I4MTD)2](F3CSO3)4 (C1), [FeII2(I4MTD)2](ClO4) [...] Read more.
Herein we report the synthesis and characterization of three new dinuclear iron(II) complexes [FeII2(I4MTD)2](F3CSO3)4 (C1), [FeII2(I4MTD)2](ClO4)4 (C2) and [FeII2(I4MTD)2](BF4)4 (C3) based on the novel ligand (I4MTD = 2,5-bis{[(1H-imidazol-4-ylmethyl)amino]methyl}-1,3,4-thiadiazole). Magnetic susceptibility measurements and single-crystal structure analysis show that the iron(II) spin centers for all complexes are in the high spin state at high temperatures. While the magnetic data of air-dried samples confirm the [HS-HS] state for C1 and C2 down to very low temperature, for C3, a gradual spin crossover is observed below 150 K. The crystal structure of C3·THF at 100 K shows that a spin transition from [HS-HS] to an intermediate state takes place, which is a 1:1 mixture of discrete [HS-HS] and [LS-LS] molecules, as identified unambiguously by crystallography. The different SCO properties of C1–C3 can be attributed to crystal packing effects in the solid state. Full article
(This article belongs to the Special Issue Coordination Polymers)
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Review

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19 pages, 4490 KiB  
Review
Spin Crossover in New Iron(II) Coordination Compounds with Tris(pyrazol-1-yl)Methane
by Olga G. Shakirova and Ludmila G. Lavrenova
Crystals 2020, 10(9), 843; https://doi.org/10.3390/cryst10090843 - 22 Sep 2020
Cited by 23 | Viewed by 3121
Abstract
We review here new advances in the synthesis and investigation of iron(II) coordination compounds with tris(pyrazol-1-yl)methane and its derivatives as ligands. The complexes demonstrate thermally induced spin crossover accompanied by thermochromism. Factors that influence the nature and temperature of the spin crossover are [...] Read more.
We review here new advances in the synthesis and investigation of iron(II) coordination compounds with tris(pyrazol-1-yl)methane and its derivatives as ligands. The complexes demonstrate thermally induced spin crossover accompanied by thermochromism. Factors that influence the nature and temperature of the spin crossover are discussed. Full article
(This article belongs to the Special Issue Coordination Polymers)
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