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Crystals
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Mixed-Metal Coordination Polymers
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Mixed-Metal Coordination Polymers

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

Deadline for manuscript submissions: closed (15 May 2023) | Viewed by 8269

Special Issue Editor

Prof. Dr. Ulli Englert

E-Mail Website
Guest Editor
Formerly Professor of Institute of Inorganic Chemistry, Rheinisch-Westfalische Technische Hochschule Aachen, 52062 Aachen, Germany
Interests: coordination polymers; ditopic ligands; phase transitions; high resolution studies; experimental charge density; sigma hole interactions; neutron diffraction; chirality in the solid state

Special Issue Information

Dear Colleagues,

Coordination polymers combine metal cations with a plethora of linking ligands and thus represent a huge class of compounds. The resulting extended structures suggest a variety of potential applications and are often associated with fascinating and highly esthetic architectures. The majority of structurally characterized coordination polymers are based on a single type of coordination center. The concomitant presence of two or more cations, statistically distributed or in a well-ordered arrangement, implies additional synthetic and analytic challenges but also offers access to new topologies and unprecedented functionality. This Special Issue is dedicated to such more complex mixed-metal coordination polymers. Diffraction methods are doubtlessly a cornerstone for their characterization, and therefore Crystals is a matching forum for their discussion. We are looking forward to your contributions addressing ligand design, cation selection, syntheses, characterization and applications of coordination polymers incorporating more than one type of cation. 

Prof. Dr. Ulli Englert
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. 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 2100 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 polymers
  • cation distribution
  • extended structures
  • ligand selectivity
  • ditopic linkers
  • functional polymers
  • topology

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Published Papers (6 papers)

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Editorial

Jump to: Research

2 pages, 158 KiB  
Editorial
Mixed-Metal Coordination Polymers
by Ulli Englert
Crystals 2024, 14(9), 785; https://doi.org/10.3390/cryst14090785 - 3 Sep 2024
Viewed by 285
Abstract
The higher degree of heterogeneity of the target compounds opens yet another dimension in the already broad field of coordination chemistry [...] Full article
(This article belongs to the Special Issue Mixed-Metal Coordination Polymers)

Research

Jump to: Editorial

15 pages, 4059 KiB  
Article
Structure Guiding Supramolecular Assemblies in Metal-Organic Multi-Component Compounds of Mn(II): Experimental and Theoretical Studies
by Manjit K. Bhattacharyya, Kamal K. Dutta, Pranay Sharma, Rosa M. Gomila, Miquel Barceló-Oliver and Antonio Frontera
Crystals 2023, 13(5), 837; https://doi.org/10.3390/cryst13050837 - 18 May 2023
Cited by 4 | Viewed by 1314
Abstract
Two multi-component coordination compounds of Mn(II), viz. [Mn(H2O)6](2-Mepy)2(4-NO2bz)2·2H2O (1) and [Mn(H2O)6][Mn(2,3-PDCH)3]2 (2) (where, 2-Mepy = 2-methylpyridine, 4-NO2bz = [...] Read more.
Two multi-component coordination compounds of Mn(II), viz. [Mn(H2O)6](2-Mepy)2(4-NO2bz)2·2H2O (1) and [Mn(H2O)6][Mn(2,3-PDCH)3]2 (2) (where, 2-Mepy = 2-methylpyridine, 4-NO2bz = 4-nitrobenzoate, 2,3-PDC = 2,3-pyridinedicarboxylate), have been synthesized and characterized using elemental, spectroscopic (FT-IR and electronic), TGA and single-crystal X-ray diffraction analyses. Complex 1 is a co-crystal hydrate of Mn(II) involving uncoordinated 2-Mepy, 4-NO2bz and water molecules; while compound 2 is a multi-component molecular complex salt of Mn(II) comprising cationic [Mn(H2O)6]2+ and anionic [Mn(2,3-PDCH)3]−complex moieties. The uncoordinated 2-Mepy and 4-NO2bz moieties of 1 are involved in lone-pair (l.p)-π and C–H⋯π interactions which stabilize the layered assembly of the compound. The crystal structure of compound 2 has been previously reported. However, we have explored the unusual enclathration of complex cationic moieties within the supramolecular host cavities formed by the molecular assembly of complex anionic moieties. The supramolecular assemblies obtained in the crystal structure have been further studied theoretically using DFT calculations, quantum theory of atoms-in-molecules (QTAIM) and non-covalent interaction plot (NCI plot) computational tools. Theoretical studies reveal that the combination of π-staking interactions (l.p-π, π-π and C–H···π) have more structure-guiding roles compared to the H-bonds. The large binding energy of π-stacking interactions in 2 is due to the antiparallel orientation of aromatic rings and their coordination to the metal centers, thereby increasing the contribution of the dipole–dipole interactions. Full article
(This article belongs to the Special Issue Mixed-Metal Coordination Polymers)
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10 pages, 2545 KiB  
Communication
Crystal Structures of 3,3′,5,5′-Tetrabromo-4,4′-bipyridine and Co(II) Coordination Polymer Based Thereon
by Ilyas F. Sakhapov, Almaz A. Zagidullin, Alexey B. Dobrynin, Igor A. Litvinov, Dmitry G. Yakhvarov, Mikhail A. Bondarenko, Alexander S. Novikov, Vladimir P. Fedin and Sergey A. Adonin
Crystals 2023, 13(4), 704; https://doi.org/10.3390/cryst13040704 - 20 Apr 2023
Cited by 2 | Viewed by 1796
Abstract
The crystal structure of 3,3′,5,5′-tetrabromo-4,4′-bipyridine (BrBipy, 1) was determined, and the features of non-covalent interactions in solid state were investigated by theoretical methods. Using BrBipy as a linker ligand, 1D coordination polymer {[Co(BrBipy)(NO3)2(CH3OH)2]} (2) was obtained and characterized. Full article
(This article belongs to the Special Issue Mixed-Metal Coordination Polymers)
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12 pages, 2425 KiB  
Article
Mixed Metal Phosphonates: Structure and Proton Conduction Manipulation through Various Alkaline Earth Metal Ions
by Song-Song Bao, Nan-Zhu Li, Yu-Xuan Wu and Yang Shen
Crystals 2022, 12(11), 1648; https://doi.org/10.3390/cryst12111648 - 16 Nov 2022
Cited by 1 | Viewed by 1216
Abstract
Three new layered mixed metal phosphonates [CoMg(notpH2)(H2O)2]ClO4·nH2O (CoMg·nH2O), [Co2Sr2(notpH2)2(H2O)5](ClO4)2·nH2O (CoSr·nH [...] Read more.
Three new layered mixed metal phosphonates [CoMg(notpH2)(H2O)2]ClO4·nH2O (CoMg·nH2O), [Co2Sr2(notpH2)2(H2O)5](ClO4)2·nH2O (CoSr·nH2O), and [CoBa(notpH2)(H2O)1.5]ClO4 (CoBa) were synthesized by reacting a tripodal metalloligand CoIII(notpH3) [notpH6 = C9H18N3(PO3H2)3] with alkaline earth metal ions. Along with an increase in the radius of the alkaline earth metal ions, the 6-coordinate {MgO6}, 7-coordinate {SrO7}, and 9-coordinate {BaO9} geometries are the distorted octahedron, capped triangular prism, and tricapped triangular prism, respectively. Consequently, the metalloligand Co(notpH2)− adopts variable coordination modes to bind the alkaline earth metal nodes, forming diverse layer topologies in the three mixed metal phosphonates. The AC impedance measurements revealed that the proton conductivities at 25 °C and 95% relative humidity (RH) follow the sequence: CoMg·nH2O > CoSr·nH2O > CoBa. As expected, CoMg·nH2O exhibits a 28-fold enhanced value for proton conductivity (4.36 × 10−4 S cm−1) compared with the previously reported isostructural compound, CoCa·nH2O, at 25 °C and 95% RH due to the greater Lewis acid strength of Mg(II) lowering the pKa of the coordinated water. Full article
(This article belongs to the Special Issue Mixed-Metal Coordination Polymers)
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12 pages, 3484 KiB  
Article
New As-Rich Arsenato-Polyoxovanadate Clusters: Solvothermal Synthesis and Selected Properties of [V6IVAs8IIIO26]4− Cluster-Containing Compounds
by Maren Rasmussen, Christian Näther and Wolfgang Bensch
Crystals 2022, 12(10), 1473; https://doi.org/10.3390/cryst12101473 - 18 Oct 2022
Cited by 2 | Viewed by 1370
Abstract
Three new arsenato-polyoxovanadates with the composition [M(en)3]2[V6As8O26] (M = Co2+ (I), Zn2+ (II), and Cd2+ (III)) were synthesized under solvothermal conditions in high yields, thus significantly enhancing the knowledge of [...] Read more.
Three new arsenato-polyoxovanadates with the composition [M(en)3]2[V6As8O26] (M = Co2+ (I), Zn2+ (II), and Cd2+ (III)) were synthesized under solvothermal conditions in high yields, thus significantly enhancing the knowledge of As-rich polyoxovanadate cluster chemistry. The compounds are isostructural and feature the very rare [V6IVAs8IIIO26]4− cluster anion. The cluster shell is constructed by interconnection of two trimeric {V3O11} groups consisting of three edge-sharing VO5 polyhedra and four As2O5 units, which are formed by two corner-sharing AsO3 pyramids. While the As2O5 group is a common structural feature in arsenato-polyoxovanadates, the {V3O11} unit is only observed in V-rich high-nuclear heteroatom-containing polyoxovanadates {V14E8} (E = As, Sb, Ge). The complexes adopt the Λ (δδδ) conformation, which is the most stable arrangement. Interestingly, the unit cell parameters do not scale with the volume of the [M(en)3]2+ complexes, assuming a constant volume of the anion. Only a very detailed Hirshfeld surface analysis revealed that the van der Waals volume of the {V6As8O26} moiety is the smallest for the Cd-containing compound, while the volumes of the anions in the other two compounds are very similar. Therefore, the observed trends of the lattice parameters can be explained on the basis of these findings. Furthermore, intermolecular interactions include As⋯H contacts in addition to O⋯H and H⋯H interactions. The electronic spectrum of I contains d–d transitions of the vanadyl group and of the Co2+ cation. As expected only the d–d transitions of the VO2+ unit occur for II and III. Full article
(This article belongs to the Special Issue Mixed-Metal Coordination Polymers)
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10 pages, 7661 KiB  
Article
Coordination of a Pyrazole Functionalized Acetylacetone to the Coinage Metal Cations: An Unexpected Packing Similarity and a Trinuclear CuII/AuI Complex
by Steven van Terwingen, Ben Ebel, Noah Nachtigall and Ulli Englert
Crystals 2022, 12(7), 984; https://doi.org/10.3390/cryst12070984 - 15 Jul 2022
Cited by 1 | Viewed by 1544
Abstract
The heteroditopic molecule HacacMePz combines a Pearson hard acetylacetone donor site with a softer trimethylpyrazole and shows site selectivity towards the coinage metal cations. The coordination of the N donor function was achieved towards AgI and AuI, leading to the [...] Read more.
The heteroditopic molecule HacacMePz combines a Pearson hard acetylacetone donor site with a softer trimethylpyrazole and shows site selectivity towards the coinage metal cations. The coordination of the N donor function was achieved towards AgI and AuI, leading to the salt [Ag(HacacMePz)2]PF6 (1) and the neutral complex [AuCl(HacacMePz)] (2). In either case, linear coordination about the coinage metal cation is observed. Interestingly, both complexes crystallize in space group Pbca with similar cell parameters. The two solids do not qualify as isostructural, albeit being closely related in real and reciprocal space. To probe the ligand’s ability for the envisaged synthesis of bimetallic coordination polymers, the mixed-metal CuII/AuI complex [Cu(acacMePzAuCl)2] (3) was obtained. In this mixed-metal oligomer, the central CuII cation adopts a square planar coordination environment with two O,O′-coordinated acacMePz− ligands, whose softer N donor sites are saturated with a AuCl moiety. Full article
(This article belongs to the Special Issue Mixed-Metal Coordination Polymers)
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