Special Issue "Structural Design and Properties of Coordination Polymers"

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

Deadline for manuscript submissions: closed (20 November 2017)

Printed Edition Available!
A printed edition of this Special Issue is available here.

Special Issue Editor

Guest Editor
Dr. George E. Kostakis

Department of Chemistry, School of Life Sciences, University of Sussex, Brighton BN1 9QJ, Sussex, UK
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Interests: 3d/4f; coordination chemistry; coordination clusters; coordination polymers; polynuclear inorganic clusters topology; topology

Special Issue Information

Dear Celleagues,

The assembly of organic ligands and metal centres yields coordination polymers, many of which find applications in conductivity, catalysis, magnetism, gas sorption, biological sensing and luminescence. The structure and topology of coordination polymers may be manipulated by changing the reaction conditions, leading to a large variety of structurally and topologically unique products. However, controlling and predicting the final outcome of the self-assembly procedure remains one of the major challenges in the field. The final products are often strongly influenced by factors such as the behaviour of a functional group in a molecule, the influence of the crystallization conditions and the various conformations of the components within the crystal.

This Special Issue aims to cover a broad range of subjects in coordination polymer chemistry, which are important to the continued growth of the field, showcase current developments and realise its full potential in applications to address major societal challenges.

Therefore, we invite you to contribute a research article to this Special Issue and provide a clear snapshot of your research in this field.

Dr. George E. Kostakis
Guest Editor

Manuscript Submission Information

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Keywords

  • Structural Design and Topological studies

  • Catalysis

  • Health and medical applications

  • Electronic and magnetic properties

Published Papers (10 papers)

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Research

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Open AccessArticle Anthracene-Based Lanthanide Metal-Organic Frameworks: Synthesis, Structure, Photoluminescence, and Radioluminescence Properties
Crystals 2018, 8(1), 53; https://doi.org/10.3390/cryst8010053
Received: 11 December 2017 / Revised: 10 January 2018 / Accepted: 17 January 2018 / Published: 22 January 2018
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Abstract
Four anthracene-based lanthanide metal-organic framework structures (MOFs) were synthesized from the combination of the lanthanide ions, Eu3+, Tb3+, Er3+, and Tm3+, with 9,10-anthracenedicarboxylic acid (H2ADC) in dimethylformamide (DMF) under hydrothermal conditions. The 3-D
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Four anthracene-based lanthanide metal-organic framework structures (MOFs) were synthesized from the combination of the lanthanide ions, Eu3+, Tb3+, Er3+, and Tm3+, with 9,10-anthracenedicarboxylic acid (H2ADC) in dimethylformamide (DMF) under hydrothermal conditions. The 3-D networks crystalize in the triclinic system with P-1 space group with the following compositions: (i) {{[Ln2(ADC)3(DMF)4·DMF]}n, Ln = Eu (1) and Tb (2)} and (ii) {{[Ln2(ADC)3(DMF)2(OH2)2·2DMF·H2O]}n, Ln = Er (3) and Tm (4)}. The metal centers exist in various coordination environments; nine coordinate in (i), while seven and eight coordinate in (ii). The deprotonated ligand, ADC, assumes multiple coordination modes, with its carboxylate functional groups severely twisted away from the plane of the anthracene moiety. The structures show ligand-based photoluminescence, which appears to be significantly quenched when compared with that of the parent H2ADC solid powder. Structure 2 is the least quenched and showed an average photoluminescence lifetime from bi-exponential decay of 0.3 ns. On exposure to ionizing radiation, the structures show radioluminescence spectral features that are consistent with the isolation of the ligand units in its 3-D network. The spectral features vary among the 3-D networks and appear to suggest that the latter undergo significant changes in their molecular and/or electronic structure in the presence of the ionizing radiation. Full article
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Open AccessArticle A 12-Fold ThSi2 Interpenetrated Network Utilizing a Glycine-Based Pseudopeptidic Ligand
Crystals 2018, 8(1), 47; https://doi.org/10.3390/cryst8010047
Received: 21 November 2017 / Revised: 4 January 2018 / Accepted: 15 January 2018 / Published: 18 January 2018
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Abstract
We report the synthesis and characterization of a 3D Cu(II) coordination polymer, [Cu3(L1)2(H2O)8]·8H2O (1), with the use of a glycine-based tripodal pseudopeptidic ligand (H3L1 = N
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We report the synthesis and characterization of a 3D Cu(II) coordination polymer, [Cu3(L1)2(H2O)8]·8H2O (1), with the use of a glycine-based tripodal pseudopeptidic ligand (H3L1 = N,N′,N″-tris(carboxymethyl)-1,3,5-benzenetricarboxamide or trimesoyl-tris-glycine). This compound presents the first example of a 12-fold interpenetrated ThSi2 (ths) net. We attempt to justify the unique topology of 1 through a systematic comparison of the synthetic parameters in all reported structures with H3L1 and similar tripodal pseudopeptidic ligands. We additionally explore the catalytic potential of 1 in the A3 coupling reaction for the synthesis of propargylamines. The compound acts as a very good heterogeneous catalyst with yields up to 99% and loadings as low as 3 mol %. Full article
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Open AccessCommunication Synthesis and Crystal Structure of a Zn(II)-Based MOF Bearing Neutral N-Donor Linker and SiF62− Anion
Crystals 2018, 8(1), 37; https://doi.org/10.3390/cryst8010037
Received: 20 November 2017 / Revised: 10 January 2018 / Accepted: 10 January 2018 / Published: 16 January 2018
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Abstract
A novel three-dimensional two-fold interpenetrated bi-porous metal-organic framework IPM-325 (IPM: IISER Pune Materials) having pcu topology was synthesized at room temperature. Single crystal X-ray diffraction (SC-XRD) study revealed that the compound crystallizes in monoclinic lattice with molecular formula {[Zn(L)2 (SiF6)]
[...] Read more.
A novel three-dimensional two-fold interpenetrated bi-porous metal-organic framework IPM-325 (IPM: IISER Pune Materials) having pcu topology was synthesized at room temperature. Single crystal X-ray diffraction (SC-XRD) study revealed that the compound crystallizes in monoclinic lattice with molecular formula {[Zn(L)2 (SiF6)] (CH2Cl2) xG}n where G = Guests). All metal centers were found to have octahedral geometry. From single crystal analysis it can be inferred that SiF62− anion play a vital role in extending the dimensionality of the framework by bridging between two metal centers. Interestingly, IPM-325 exhibited two-step structural transformation maintaining the crystallinity of the framework as characterized by powder X-ray diffraction (PXRD). Full article
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Open AccessArticle Incorporating the Thiazolo[5,4-d]thiazole Unit into a Coordination Polymer with Interdigitated Structure
Crystals 2018, 8(1), 30; https://doi.org/10.3390/cryst8010030
Received: 21 December 2017 / Revised: 5 January 2018 / Accepted: 6 January 2018 / Published: 12 January 2018
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Abstract
The linker 2,5-di(4-pyridyl)thiazolo[5,4-d]thiazole (Dptztz), whose synthesis and structure is described here, was utilized together with benzene-1,3-dicarboxylate (isophthalate, 1,3-BDC2−) for the preparation of the two-dimensional coordination network [Zn(1,3-BDC)Dptztz]·DMF (DMF = dimethylformamide) via a solvothermal reaction. Compound [Zn(1,3-BDC)Dptztz]·DMF belongs to the class of
[...] Read more.
The linker 2,5-di(4-pyridyl)thiazolo[5,4-d]thiazole (Dptztz), whose synthesis and structure is described here, was utilized together with benzene-1,3-dicarboxylate (isophthalate, 1,3-BDC2−) for the preparation of the two-dimensional coordination network [Zn(1,3-BDC)Dptztz]·DMF (DMF = dimethylformamide) via a solvothermal reaction. Compound [Zn(1,3-BDC)Dptztz]·DMF belongs to the class of coordination polymers with interdigitated structure (CIDs). The incorporated DMF solvent molecules can be removed through solvent exchange and evacuation such that the supramolecular 3D packing of the 2D networks retains porosity for CO2 adsorption in activated [Zn(1,3-BDC)Dptztz]. The first sorption study of a tztz-functionalized porous metal-organic framework material yields a BET surface of 417 m2/g calculated from the CO2 adsorption data. The heat of adsorption for CO2 exhibits a relative maximum with 27.7 kJ/mol at an adsorbed CO2 amount of about 4 cm3/g STP, which is interpreted as a gate-opening effect. Full article
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Open AccessArticle Prussian Blue Analogue Mesoframes for Enhanced Aqueous Sodium-ion Storage
Crystals 2018, 8(1), 23; https://doi.org/10.3390/cryst8010023
Received: 24 November 2017 / Revised: 22 December 2017 / Accepted: 3 January 2018 / Published: 7 January 2018
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Abstract
Mesostructure engineering is a potential avenue towards the property control of coordination polymers in addition to the traditional structure design on an atomic/molecular scale. Mesoframes, as a class of mesostructures, have short diffusion pathways for guest species and thus can be an ideal
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Mesostructure engineering is a potential avenue towards the property control of coordination polymers in addition to the traditional structure design on an atomic/molecular scale. Mesoframes, as a class of mesostructures, have short diffusion pathways for guest species and thus can be an ideal platform for fast storage of guest ions. We report a synthesis of Prussian Blue analogue mesoframes by top-down etching of cubic crystals. Scanning and transmission electron microscopy revealed that the surfaces of the cubic crystals were selectively removed by HCl, leaving the corners, edges, and the cores connected together. The mesoframes were used as a host for the reversible insertion of sodium ions with the help of electrochemistry. The electrochemical intercalation/de-intercalation of Na+ ions in the mesoframes was highly reversible even at a high rate (166.7 C), suggesting that the mesoframes could be a promising cathode material for aqueous sodium ion batteries with excellent rate performance and cycling stability. Full article
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Open AccessArticle A One-Dimensional Coordination Polymer Containing Cyclic [Ag4] Clusters Supported by a Hybrid Pyridine and Thioether Functionalized 1,2,3-Triazole
Crystals 2018, 8(1), 16; https://doi.org/10.3390/cryst8010016
Received: 7 December 2017 / Revised: 28 December 2017 / Accepted: 28 December 2017 / Published: 2 January 2018
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Abstract
A pyridine and thioether co-supported triazole ligand L (L = 2-((4-(3-(cyclopentylthio)propyl)-1H-1,2,3-triazol-1-yl)methyl)pyridine) has been synthesized using the CuAAC click reaction. This ligand supports the formation of a thermally stable, one-dimensional coordination polymer [L2Ag4]n·4n(BF4
[...] Read more.
A pyridine and thioether co-supported triazole ligand L (L = 2-((4-(3-(cyclopentylthio)propyl)-1H-1,2,3-triazol-1-yl)methyl)pyridine) has been synthesized using the CuAAC click reaction. This ligand supports the formation of a thermally stable, one-dimensional coordination polymer [L2Ag4]n·4n(BF4) (1) possessing a cationic polymeric structure with [Ag4] metallomacrocycles, in which the ligand L displays chelate/bridging coordination modes using all four potential donors of nitrogen (N) and thioether (S). The dominant direction of the prism crystals of 1 aligns with the propagation of the chain in the lattice. Full article
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Open AccessArticle Solvent Dependent Disorder in M2(BzOip)2(H2O)·Solvate (M = Co or Zn)
Crystals 2018, 8(1), 6; https://doi.org/10.3390/cryst8010006
Received: 5 December 2017 / Revised: 19 December 2017 / Accepted: 19 December 2017 / Published: 24 December 2017
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Abstract
Coordination polymers derived from 5-benzyloxy isophthalic acid (H2BzOip) are rare, with only three reported that do not contain additional bridging ligands, of which two M2(BzOip)2(H2O) (M = Co and Zn) are isomorphous. It was hoped
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Coordination polymers derived from 5-benzyloxy isophthalic acid (H2BzOip) are rare, with only three reported that do not contain additional bridging ligands, of which two M2(BzOip)2(H2O) (M = Co and Zn) are isomorphous. It was hoped that by varying the solvent system in a reaction between H2BzOip and M(OAc)2 (M = Co and Zn), from water to a water/alcohol mixture, coordination polymers of different topology could be formed. Instead, two polymorphs of the existing M2(BzOip)2(H2O) (M = Co and Zn) were isolated from aqueous methanol and aqueous ethanol, in which a small number of guest solvent molecules are present in the crystals. These guest water molecules disrupt the hexaphenyl embrace motif, leading to varying degrees of disorder of the benzyl groups. Full article
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Open AccessArticle Synthesis, Crystal Structure, Gas Absorption, and Separation Properties of a Novel Complex Based on Pr and a Three-Connected Ligand
Crystals 2017, 7(12), 370; https://doi.org/10.3390/cryst7120370
Received: 29 October 2017 / Revised: 6 December 2017 / Accepted: 7 December 2017 / Published: 11 December 2017
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Abstract
A novel Pr complex, constructed from a rigid three-connected H3TMTA and praseodymium(III) ion, has been synthesized in a mixed solvent system and characterized by X-ray single crystal diffraction, infrared spectroscopy, a thermogravimetric analysis, an element analysis, and powder X-ray diffraction, which
[...] Read more.
A novel Pr complex, constructed from a rigid three-connected H3TMTA and praseodymium(III) ion, has been synthesized in a mixed solvent system and characterized by X-ray single crystal diffraction, infrared spectroscopy, a thermogravimetric analysis, an element analysis, and powder X-ray diffraction, which reveals that complex 1 crystallizes in a three-dimensional porous framework. Moreover, the thermal stabilities and the fluorescent and gas adsorption and separation properties of complex 1 were investigated systematically. Full article
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Open AccessArticle Reversible Single-Crystal-to-Single-Crystal Structural Transformation in a Mixed-Ligand 2D Layered Metal-Organic Framework: Structural Characterization and Sorption Study
Crystals 2017, 7(12), 364; https://doi.org/10.3390/cryst7120364
Received: 20 November 2017 / Revised: 3 December 2017 / Accepted: 5 December 2017 / Published: 7 December 2017
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Abstract
A 3D supramolecular network, [Cd(bipy)(C4O4)(H2O)2]·3H2O (1) (bipy = 4,4′-bipyridine and C4O42− = dianion of H2C4O4), constructed by mixed-ligand two-dimensional (2D) metal-organic
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A 3D supramolecular network, [Cd(bipy)(C4O4)(H2O)2]·3H2O (1) (bipy = 4,4′-bipyridine and C4O42− = dianion of H2C4O4), constructed by mixed-ligand two-dimensional (2D) metal-organic frameworks (MOFs) has been reported and structurally determined by the single-crystal X-ray diffraction method and characterized by other physicochemical methods. In 1, the C4O42− and bipy both act as bridging ligands connecting the Cd(II) ions to form a 2D layered MOF, which are then extended to a 3D supramolecular network via the mutually parallel and interpenetrating arrangements among the 2D-layered MOFs. Compound 1 shows a two-step dehydration process with weight losses of 11.0% and 7.3%, corresponding to the weight-loss of three guest and two coordinated water molecules, respectively, and exhibits an interesting reversible single-crystal-to-single-crystal (SCSC) structural transformation upon de-hydration and re-hydration for guest water molecules. The SCSC structural transformation have been demonstrated and monitored by single-crystal and X-ray powder diffraction, and thermogravimetic analysis studies. Full article
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Review

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Open AccessReview Multifunctional Aromatic Carboxylic Acids as Versatile Building Blocks for Hydrothermal Design of Coordination Polymers
Crystals 2018, 8(2), 83; https://doi.org/10.3390/cryst8020083
Received: 15 January 2018 / Revised: 28 January 2018 / Accepted: 29 January 2018 / Published: 3 February 2018
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Abstract
Selected recent examples of coordination polymers (CPs) or metal-organic frameworks (MOFs) constructed from different multifunctional carboxylic acids with phenyl-pyridine or biphenyl cores have been discussed. Despite being still little explored in crystal engineering research, such types of semi-rigid, thermally stable, multifunctional and versatile
[...] Read more.
Selected recent examples of coordination polymers (CPs) or metal-organic frameworks (MOFs) constructed from different multifunctional carboxylic acids with phenyl-pyridine or biphenyl cores have been discussed. Despite being still little explored in crystal engineering research, such types of semi-rigid, thermally stable, multifunctional and versatile carboxylic acid building blocks have become very promising toward the hydrothermal synthesis of metal-organic architectures possessing distinct structural features, topologies, and functional properties. Thus, the main aim of this mini-review has been to motivate further research toward the synthesis and application of coordination polymers assembled from polycarboxylic acids with phenyl-pyridine or biphenyl cores. The importance of different reaction parameters and hydrothermal conditions on the generation and structural types of CPs or MOFs has also been highlighted. The influence of the type of main di- or tricarboxylate ligand, nature of metal node, stoichiometry and molar ratio of reagents, temperature, and presence of auxiliary ligands or templates has been showcased. Selected examples of highly porous or luminescent CPs, compounds with unusual magnetic properties, and frameworks for selective sensing applications have been described. Full article
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Graphical abstract

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