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Crystals
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Multifunctional Coordination Polymers: Synthesis, Structure, Properties and Applications
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Multifunctional Coordination Polymers: Synthesis, Structure, Properties and Applications

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

Deadline for manuscript submissions: closed (20 December 2023) | Viewed by 17653

Special Issue Editors

Prof. Dr. Ileana Dragutan

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Guest Editor
Institute of Organic Chemistry of the Romanian Academy, 202B Spl. Independentei, 060023 Bucharest, Romania
Interests: transition metals complexes and their chemistry and use in homogeneous catalysis and polymer synthesis; Ru-catalyzed olefin metathesis; metathesis driven syntheses of some bioactive compounds and metathesis-related processes; stable nitroxide free radicals and their preparation and multifarious applications using ESR
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Fu Ding

E-Mail Website
Guest Editor
College of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China
Interests: organic chemistry; analytical chemistry; organometallic chemistry; coordination chemistry; coordination polymers; spectroscopy; lanthanide chemistry; transition metal chemistry; metal–carbene complexes
Prof. Dr. Ya-Guang Sun

E-Mail Website
Guest Editor
Shenyang Economic and Technological Development Zone, Shenyang University of Chemical Technology,11th Street, Shenyang 110142, China
Interests: inorganic chemistry; coordination chemistry; coordination polymers; organometallic chemistry; transition metal chemistry; heterogeneous catalysis; lanthanide chemistry
Prof. Dr. Valerian Dragutan

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Guest Editor
Institute of Organic Chemistry of the Romanian Academy, 202B Spl. Independentei, 060023 Bucharest, Romania
Interests: organic chemistry; organic synthesis; organometallic chemistry; coordination complexes; catalysis; free radicals; metathesis chemistry; polymerization chemistry
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

This Special Issue of Crystals is dedicated to multifunctional coordination polymers (CPs), aiming to disclose the most recent developments related to the design, synthesis, structure and properties of these high-value and multifunctional hybrid materials. As an attractive class of coordination polymers, metal–organic frameworks (MOFs) will also be considered, with emphasis on their emerging applications in modern areas of science and technology.

The unprecedented physical–chemical properties of coordination polymers and MOFs have been fully evidenced by their specific micro- and nanocrystalline structure, large surface area, permanent porosity, excellent electrical, optical and magnetic abilities, and an increased robustness and stability, enabling them to be an extremely interesting class of materials for diverse practical utilizations. By tuning their physical–chemical properties through a proper choice of metal nodes and functional organic ligands, this type of hybrid material has been successfully developed, already readily applied in many demanding areas following current trends of science and technology, such as gas adsorption and separation, energy storage, water purification, luminescent appliances, enhanced electrical conductance, optical and magnetic devices, chemical, biological and thermal sensing, biomedical imaging and drug delivery. The postsynthesis modification and treatment of coordination polymers with different transition metal salts (inducing beneficial catalytic properties), enables them to be deeply integrated as heterogeneous catalysts with enhanced reactivity and selectivity in diverse chemical processes such as carbon–carbon bond-formation, CO2 capture and conversion, water splitting, hydrogen evolution and various reduction and oxidation processes.

With the aim of unveiling the most recent scientific achievements in this rapidly growing domain of chemistry, we particularly welcome short communications, full papers and comprehensive reviews related to the synthesis, spectral characterization, X-ray crystallography, crystal structure, physical–chemical properties and applications of coordination polymers and MOFs for this Special Issue of Crystals. Selected contributions regarding the present developments and future perspectives in modern areas, e.g., gas adsorption and separation, energy storage, water purification, hydrogen evolution, heterogeneous catalysis, luminescence, magnetism, electrical conductance, optical devices, chemical, biological and thermal sensing, environmental remediation, biomedical imaging and applications, and drug delivery systems, would be highly appreciated.

Prof. Dr. Ileana Dragutan
Prof. Dr. Fu Ding
Prof. Dr. Ya-Guang Sun
Prof. Dr. Valerian Dragutan
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

  • coordination polymers
  • metal–organic frameworks
  • metal clusters
  • organic ligands
  • transition metals
  • postsynthetic modification
  • crystal structure
  • powder X-ray diffraction
  • molecular storage
  • energy storage
  • water splitting
  • hydrogen evolution
  • luminescence
  • magnetism
  • heterogeneous catalysis

Published Papers (13 papers)

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Editorial

Jump to: Research, Review

7 pages, 210 KiB  
Editorial
Recent Developments in Multifunctional Coordination Polymers
by Ileana Dragutan, Fu Ding, Yaguang Sun and Valerian Dragutan
Crystals 2024, 14(4), 301; https://doi.org/10.3390/cryst14040301 - 25 Mar 2024
Viewed by 692
Abstract
This Special Issue of Crystals “Multifunctional Coordination Polymers: Synthesis, Structure, Properties and Applications” [...] Full article
(This article belongs to the Special Issue Multifunctional Coordination Polymers: Synthesis, Structure, Properties and Applications)

Research

Jump to: Editorial, Review

12 pages, 2992 KiB  
Article
Fabrication, Crystal Structures, Catalytic, and Anti-Wear Performance of 3D Zinc(II) and Cadmium(II) Coordination Polymers Based on an Ether-Bridged Tetracarboxylate Ligand
by Zheng-Hua Zhao, Qin Zhang, Yu-Feng Liu, Jin-Zhong Gu and Zi-Fa Shi
Crystals 2023, 13(12), 1681; https://doi.org/10.3390/cryst13121681 - 14 Dec 2023
Cited by 1 | Viewed by 850
Abstract
Two 3D Zn(II) and Cd(II) coordination polymers, [Zn2(µ4-dppa)(µ-dpe)(µ-H2O)]n·nH2O (1) and [Cd2(µ8-dppa)(µ-dpe)(H2O)]n ( [...] Read more.
Two 3D Zn(II) and Cd(II) coordination polymers, [Zn2(µ4-dppa)(µ-dpe)(µ-H2O)]n·nH2O (1) and [Cd2(µ8-dppa)(µ-dpe)(H2O)]n (2), have been constructed hydrothermally using 4-(3,5-dicarboxyphenoxy)phthalic acid (H4dppa), 1,2-di(4-pyridyl)ethylene (dpe), and zinc or cadmium chlorides. Both compounds feature 3D network structures. Their structure and topology, thermal stability, catalytic, and anti-wear properties were investigated. Particularly, excellent catalytic performance was displayed by zinc(II)-polymer 1 in the Knoevenagel condensation reaction at room temperature. Full article
(This article belongs to the Special Issue Multifunctional Coordination Polymers: Synthesis, Structure, Properties and Applications)
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14 pages, 6717 KiB  
Article
A Luminescent MOF Based on Pyrimidine-4,6-dicarboxylate Ligand and Lead(II) with Unprecedented Topology
by Laura Razquin-Bobillo, Oier Pajuelo-Corral, Andoni Zabala-Lekuona, Iñigo Vitorica-Yrezabal, Jose Angel García, Jose M. Moreno, Antonio Rodríguez-Diéguez and Javier Cepeda
Crystals 2023, 13(10), 1490; https://doi.org/10.3390/cryst13101490 - 13 Oct 2023
Cited by 1 | Viewed by 795
Abstract
In the present work, we report on a 3D MOF of {[Pb5(μ3-OH)(μ3-NO3)3(μ6-pmdc)3]·H2O}n formula (pmdc = pyrimidine-4,6-dicarboxylate) synthesized by an oven-heated, solvent-free procedure. The large connectivity afforded [...] Read more.
In the present work, we report on a 3D MOF of {[Pb5(μ3-OH)(μ3-NO3)3(μ6-pmdc)3]·H2O}n formula (pmdc = pyrimidine-4,6-dicarboxylate) synthesized by an oven-heated, solvent-free procedure. The large connectivity afforded by the three ligands in their coordination to lead(II) ions grows cubic building units characterized by a central Pb atom with an unusual coordination index of 12 and 6 pmdc ligands occupying the faces. These cubic units are linked to one another giving rise to a quite condensed structure that represents an unprecedented topology showing the (4·62)6(43)2(45·610)3(45·68·82)6(46·69)6(612·83) point symbol. The crystalline material has been characterized by routine physico-chemical techniques to confirm its purity, and its thermal behaviour has been also studied by thermogravimetric and thermodiffractometric analyses. The solid presents a greenish blue photoluminescent emission based on pmdc ligands, as revealed by time-dependent density-functional theory (TDDFT) calculations, which is substantially more intense than in the free H2pmdc ligand according to its improved quantum yield. The emissive capacity of the material is further analysed according to decreasing temperature of the polycrystalline sample, finding that sizeable, long-lasting phosphorescence is present. Full article
(This article belongs to the Special Issue Multifunctional Coordination Polymers: Synthesis, Structure, Properties and Applications)
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16 pages, 4917 KiB  
Article
Synthesis, X-ray Structure and Hirshfeld Surface Analysis of Zn(II) and Cd(II) Complexes with s-Triazine Hydrazone Ligand
by Saied M. Soliman, Ayman El-Faham, Assem Barakat, Alexandra M. Z. Slawin, John Derek Woollins and Morsy A. M. Abu-Youssef
Crystals 2023, 13(8), 1232; https://doi.org/10.3390/cryst13081232 - 10 Aug 2023
Cited by 1 | Viewed by 740
Abstract
The two group IIB complexes [Cd(DMPT)Cl2] (6) and [Zn(DMPT)Cl2] (7) of the tridentate ligand (DMPT), 2,4-bis(morpholin-4-yl)-6-[(E)-2-[1-(pyridin-2-yl) ethylidene]hydrazin-1-yl]-1,3,5-triazine were synthesized, and their structural aspects were elucidated with the aid of X-ray crystallography. [...] Read more.
The two group IIB complexes [Cd(DMPT)Cl2] (6) and [Zn(DMPT)Cl2] (7) of the tridentate ligand (DMPT), 2,4-bis(morpholin-4-yl)-6-[(E)-2-[1-(pyridin-2-yl) ethylidene]hydrazin-1-yl]-1,3,5-triazine were synthesized, and their structural aspects were elucidated with the aid of X-ray crystallography. Both complexes crystallized in the monoclinic crystal system, with P21/n as a space group. The unit cell parameters for 6 are a = 14.1563(9) Å, b = 9.4389(6) Å, c = 16.5381(11) Å and β = 91.589(5)° while the respective values for 7 are 11.3735(14), 13.8707(13), 14.9956(16), and 111.646(2)°. The unit cell volume is slightly less (2198.9(4) Å3) in complex 7 compared to complex 6 (2209.0(2) Å3). Both complexes have a penta-coordination environment around the metal ion, where the DMPT ligand acts as a neutral tridentate NNN-chelate via the pyridine, hydrazone, and one of the s-triazine N-atoms. The penta-coordination environment of the Cd(II) in complex 6 is close to a square pyramidal configuration with some distortion. On the other hand, the ZnN3Cl2 coordination environment is highly distorted and located intermediately between the trigonal bipyramidal and square pyramids. Supramolecular structure analysis of 6 with the aid of Hirshfeld calculations indicated the importance of the Cl…H, O…H, and C…H interactions. Their percentages were calculated to be 20.9, 9.1, and 8.7%, respectively. For 7, the Cl…H, O…H, C…H, and N…H contacts are the most important. Their percentages are 20.3, 9.0, 7.0, and 8.4%, respectively. In both complexes, the major intermolecular interaction is the hydrogen–hydrogen interactions which contributed 45.5 and 46.6%, respectively. Full article
(This article belongs to the Special Issue Multifunctional Coordination Polymers: Synthesis, Structure, Properties and Applications)
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14 pages, 3600 KiB  
Article
A Novel Na(I) Coordination Complex with s-Triazine Pincer Ligand: Synthesis, X-ray Structure, Hirshfeld Analysis, and Antimicrobial Activity
by Amal Yousri, Ayman El-Faham, Matti Haukka, Mohammed Salah Ayoup, Magda M. F. Ismail, Nagwan G. El Menofy, Saied M. Soliman, Lars Öhrström, Assem Barakat and Morsy A. M. Abu-Youssef
Crystals 2023, 13(6), 890; https://doi.org/10.3390/cryst13060890 - 29 May 2023
Cited by 3 | Viewed by 1343
Abstract
The pincer ligand 2,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)-6-methoxy-1,3,5-triazine (bpmt) was used to synthesize the novel [Na(bpmt)2][AuCl4] complex through the self-assembly method. In this complex, the Na(I) ion is hexa-coordinated with two tridentate N-pincer ligands (bpmt [...] Read more.
The pincer ligand 2,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)-6-methoxy-1,3,5-triazine (bpmt) was used to synthesize the novel [Na(bpmt)2][AuCl4] complex through the self-assembly method. In this complex, the Na(I) ion is hexa-coordinated with two tridentate N-pincer ligands (bpmt). The two bpmt ligand units are meridionally coordinated to Na(I) via one short Na-N(s-triazine) and two slightly longer Na-N(pyrazole) bonds, resulting in a distorted octahedral geometry around the Na(I) ion. In the coordinated bpmt ligand, the s-triazine core is not found to be coplanar with the two pyrazole moieties. Additionally, the two bpmt units are strongly twisted from one another by 64.94°. Based on Hirshfeld investigations, the H···H (53.4%) interactions have a significant role in controlling the supramolecular arrangement of the [Na(bpmt)2][AuCl4] complex. In addition, the Cl···H (12.2%), C···H (11.5%), N···H (9.3%), and O···H (4.9%) interactions are significant. Antimicrobial investigations revealed that the [Na(bpmt)2][AuCl4] complex has promising antibacterial and antifungal activities. The [Na(bpmt)2][AuCl4] complex showed enhanced antibacterial activity for the majority of the studied gram-positive and gram-negative bacteria compared to the free bpmt (MIC = 62.5–125 µg/mL vs. MIC = 62.5–500 µg/mL, respectively) and Amoxicillin (MIC > 500 µg/mL) as a positive control. Additionally, the [Na(bpmt)2][AuCl4] complex had better antifungal efficacy (MIC = 125 µg/mL) against C. albicans compared to bpmt (MIC = 500 µg/mL). Full article
(This article belongs to the Special Issue Multifunctional Coordination Polymers: Synthesis, Structure, Properties and Applications)
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17 pages, 6723 KiB  
Article
Influence of the Arene/Perfluoroarene Ratio on the Structure and Non-Covalent Interactions in Crystals of Cd(II), Cd(II)-Tb(III) and Cu(II) Compounds
by Julia K. Voronina, Dmitriy S. Yambulatov, Aleksander S. Chistyakov, Alena E. Bolot’ko, Leonid M. Efromeev, Maxim A. Shmelev, Alexey A. Sidorov and Igor L. Eremenko
Crystals 2023, 13(4), 678; https://doi.org/10.3390/cryst13040678 - 14 Apr 2023
Cited by 2 | Viewed by 1249
Abstract
The influence of arene/perfluoroarene ratio on the structure and crystal packing of carboxylate and nitrate-carboxylate complexes of Cd, Cd-Tb and Cu was studied, using the following compounds: pentafluorobenzoate (pfb) and 4-allyl-2,3,5,6-tetrabenzoate (Afb) anions and 1,10-phenanthroline (phen) composition [Cd(pfb)2(phen)]n (1 [...] Read more.
The influence of arene/perfluoroarene ratio on the structure and crystal packing of carboxylate and nitrate-carboxylate complexes of Cd, Cd-Tb and Cu was studied, using the following compounds: pentafluorobenzoate (pfb) and 4-allyl-2,3,5,6-tetrabenzoate (Afb) anions and 1,10-phenanthroline (phen) composition [Cd(pfb)2(phen)]n (1), [Cd(NO3)(pfb)(phen)]n (2), [Tb2Cd2(pfb)10(phen)2]. 3MeCN]n (3), [Tb2Cd2(NO3)2(pfb)8(phen)2.1.5MeCN]n (4), [Cu2(Afb)4(phen)2] (5), [Cu2(NO3)2(Afb)2(phen)2] (6). It is shown that the main contribution to the stabilization of the crystal packing of coordination polymers 1–4 and molecular binuclear complexes 5 and 6 can be attributed to non-covalent π···π, C-H···F, and C-F···π interactions. It was found that the partial exchange of pfb or Afb anions on compact NO3− anions leads to a decrease in steric hindrance, a more efficient overlap of aromatic fragments, and a significant change in the geometry of complexes. Synthesized compounds were characterized by X-ray diffraction analysis, IR spectroscopy, and CHN analysis. The thermal stability of complexes 1 and 2 was studied. Non-covalent interactions were analyzed using the Hirshfeld surface method. Full article
(This article belongs to the Special Issue Multifunctional Coordination Polymers: Synthesis, Structure, Properties and Applications)
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10 pages, 2843 KiB  
Article
N-Heterocyclic Carbene–Palladium Functionalized Coordination Polymer (Pd-NHC@Eu-BCI) as an Efficient Heterogeneous Catalyst in the Suzuki–Miyaura Coupling Reaction
by Lixin You, Rui Tan, Xiaojuan Wang, Jianhong Hao, Shiyu Xie, Gang Xiong, Fu Ding, Andrei S. Potapov and Yaguang Sun
Crystals 2023, 13(2), 341; https://doi.org/10.3390/cryst13020341 - 17 Feb 2023
Cited by 2 | Viewed by 1366
Abstract
In the present work, a new heterogeneous catalyst Pd-NHC@Eu-BCI was synthesized by introducing N-heterocyclic carbene–palladium active sites into a 2D coordination polymer [Eu(BCI)(NO3)2H2O]n (Eu-BCI) based on a 1,3-bis(carboxymethyl)imidazolium (HBCI) ligand. The catalyst was characterized by various [...] Read more.
In the present work, a new heterogeneous catalyst Pd-NHC@Eu-BCI was synthesized by introducing N-heterocyclic carbene–palladium active sites into a 2D coordination polymer [Eu(BCI)(NO3)2H2O]n (Eu-BCI) based on a 1,3-bis(carboxymethyl)imidazolium (HBCI) ligand. The catalyst was characterized by various analytical techniques such as X-ray photoelectron spectroscopy (XPS), inductively coupled plasma atomic emission spectroscopy (ICP-AES), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (PXRD), infrared spectroscopy (IR) and thermogravimetric analysis (TGA). Catalytic activity of Pd-NHC@Eu-BCI was tested for the Suzuki–Miyaura cross-coupling reaction. The catalyst from the reaction mixture was easily recovered by filtration and still exhibited good catalytic activity and maintained its original structure after five cycles. Full article
(This article belongs to the Special Issue Multifunctional Coordination Polymers: Synthesis, Structure, Properties and Applications)
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10 pages, 1748 KiB  
Article
A Rare Structural Motif for a Luminescent Cu(I) Coordination Polymer with 3-(Pyridin-2-yl)triimidazotriazine
by Daniele Malpicci, Delia Blasi, Daniele Marinotto, Alessandra Forni, Elena Cariati, Elena Lucenti and Lucia Carlucci
Crystals 2023, 13(1), 149; https://doi.org/10.3390/cryst13010149 - 14 Jan 2023
Cited by 2 | Viewed by 1607
Abstract
The coordination ability of the pyridine derivative of cyclic triimidazole, namely 3-(pyridin-2-yl)triimidazotriazine (TT-Py) towards Cu(I) was explored. TT-Py is an appealing nitrogen-rich ligand characterized by the presence of three imidazole nitrogen atoms with trigonal symmetry and a pyridine moiety, available for [...] Read more.
The coordination ability of the pyridine derivative of cyclic triimidazole, namely 3-(pyridin-2-yl)triimidazotriazine (TT-Py) towards Cu(I) was explored. TT-Py is an appealing nitrogen-rich ligand characterized by the presence of three imidazole nitrogen atoms with trigonal symmetry and a pyridine moiety, available for coordination to metal ions. The multidentate nature of TT-Py allows to isolate, by reaction with CuI at room temperature, the one-dimensional coordination network [Cu2I2(TT-Py)]n (1). 1 is characterized by a rare structural network built-up by the combination in a 1:2 ratio of two common motifs for Cu(I) halides coordination polymers, which are the double-stranded stair and the zig-zag chain. 1 displays one broad long-lived emission in the solid state, which has been associated, by the support of DFT and TDDFT calculation, with low-energy transitions of MLCT or XMLCT character. Full article
(This article belongs to the Special Issue Multifunctional Coordination Polymers: Synthesis, Structure, Properties and Applications)
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17 pages, 3563 KiB  
Article
Anion Influence on Supramolecular Interactions in Exo-Coordinated Silver(I) Complexes with N2O2 Schiff Base Macrocycle
by Franc Perdih, Milenko Korica, Lorena Šebalj and Tomislav Balić
Crystals 2023, 13(1), 50; https://doi.org/10.3390/cryst13010050 - 27 Dec 2022
Viewed by 1591
Abstract
Silver(I) complexes with aza-oxa macrocyclic Schiff bases L (L = 1,5-diaza-2,4:7,8:16,17-tribenzo-9,15-dioxa-cyclooctadeca-1,5-dien) were prepared by the reaction of the corresponding macrocycle with four different silver salts (AgX; X = ClO4, PF6, SbF6 and BF4). In all four [...] Read more.
Silver(I) complexes with aza-oxa macrocyclic Schiff bases L (L = 1,5-diaza-2,4:7,8:16,17-tribenzo-9,15-dioxa-cyclooctadeca-1,5-dien) were prepared by the reaction of the corresponding macrocycle with four different silver salts (AgX; X = ClO4, PF6, SbF6 and BF4). In all four compounds, silver ions are exo-coordinated by two neighboring ligand molecules in linear and T-shaped geometries. Such a coordination mode results in the formation of infinite 1D polymeric chains. Compounds AgLClO4 and AgLBF4 are isostructural, and polymeric chains display 1D zigzag topology. In AgLPF6 there are three symmetrically unique Ag ions in the asymmetric unit of the compound. Two silver ions are linearly coordinated with two neighboring ligand molecules and are part of a discrete polymer chain. The third silver ion is coordinated with two ligand molecules and a methanol molecule in a T-shaped geometry. Such coordination geometry results in the formation of two discrete infinite polymer chains in the crystal structure. In the AgLSbF6 compound, the chain topology is a linear zigzag chain, but in this compound, there is a difference in the orientation of the Ag-N bond. The Ag-N-Ag bonds are in the trans position relative to the plane calculated through the ligand molecule, while the Ag-N bonds are in the cis position in all other compounds. Due to the presence of a bulky SbF6 anion, the ligand molecule is planar compared to other compounds. Considering intermolecular interactions, there is a huge variety of different interactions, mostly depending on the type of anion. A general supramolecular motif in all compounds is best described as 2D sheets of ligand–metal polymers with anions and solvent molecules sandwiched between them. In addition, the obtained compounds were characterized by IR spectroscopy and thermal analysis. The TG analysis indicates a rather surprising and considerable thermal stability of the prepared compounds, with some compounds thermally stable over 300 °C. Full article
(This article belongs to the Special Issue Multifunctional Coordination Polymers: Synthesis, Structure, Properties and Applications)
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9 pages, 2855 KiB  
Article
Synthesis, Crystal Structure, and Optical Properties of a Trinuclear Zinc(II) Complex with Rhodamine B
by Mihai Răducă, Sorana Ionescu and Augustin M. Mădălan
Crystals 2022, 12(12), 1813; https://doi.org/10.3390/cryst12121813 - 13 Dec 2022
Viewed by 1411
Abstract
A heteroleptic homotrinuclear complex, [Zn3(valhydr)2(RhB)2(EtOH)2](ClO4)2 (H2valhydr = 1,2-bis(2-hydroxy-3-methoxybenzylidene)hydrazine, RhB = rhodamine B), was synthesized and structurally characterized by X-ray diffraction on single crystal. In the centrosymmetric complex, the zinc ions [...] Read more.
A heteroleptic homotrinuclear complex, [Zn3(valhydr)2(RhB)2(EtOH)2](ClO4)2 (H2valhydr = 1,2-bis(2-hydroxy-3-methoxybenzylidene)hydrazine, RhB = rhodamine B), was synthesized and structurally characterized by X-ray diffraction on single crystal. In the centrosymmetric complex, the zinc ions are positioned in a linear manner. The external zinc ions are pentacoordinated with a distorted square pyramidal stereochemistry, while the central zinc ion presents an elongated octahedral geometry. Luminescent properties of the complex were investigated in solid state and solution. Full article
(This article belongs to the Special Issue Multifunctional Coordination Polymers: Synthesis, Structure, Properties and Applications)
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13 pages, 2850 KiB  
Article
Anion-Dependent Cu(II) Coordination Polymers: Geometric, Magnetic and Luminescent Properties
by Ihsan Ullah, Jong Won Shin, Ryuya Tokunaga, Shinya Hayami, Hye Jin Shin and Kil Sik Min
Crystals 2022, 12(8), 1096; https://doi.org/10.3390/cryst12081096 - 05 Aug 2022
Viewed by 1751
Abstract
A one-dimensional (1D) coordination polymer [Cu2(bpba)(CH3COO)4] (1) and a two-dimensional (2D) coordination polymer [Cu(bpba)2(H2O)(NO3)](NO3)∙2H2O∙MeOH (2) were synthesized by the reaction between Cu(CH3 [...] Read more.
A one-dimensional (1D) coordination polymer [Cu2(bpba)(CH3COO)4] (1) and a two-dimensional (2D) coordination polymer [Cu(bpba)2(H2O)(NO3)](NO3)∙2H2O∙MeOH (2) were synthesized by the reaction between Cu(CH3COO)2∙H2O/Cu(NO3)2∙3H2O and bis(4-pyridyl)benzylamine (bpba). The Cu(II) ions of 1 and 2 have distorted-square pyramidal coordination with a paddle-wheel structure and an octahedral geometry, respectively. By coordinating the Cu(II) ions and bpba ligands, 1 and 2 formed zigzag 1D and puckered 2D coordination polymers, respectively. Polymer 1 exhibits strong emissions at 355 and 466 nm, whereas polymer 2 exhibits strong emissions only at 464 nm. The emissions are strongly dependent on the geometry of the Cu(II) ions linked by the bpba and anionic ligands. Polymer 1 exhibits a very strong antiferromagnetic interaction within the paddle-wheel dimer, whereas polymer 2 exhibits a very weak antiferromagnetic interaction through the bpba linkers and/or space. Full article
(This article belongs to the Special Issue Multifunctional Coordination Polymers: Synthesis, Structure, Properties and Applications)
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25 pages, 4836 KiB  
Article
Molecular Structures of the Silicon Pyridine-2-(thi)olates Me3Si(pyX), Me2Si(pyX)2 and Ph2Si(pyX)2 (py = 2-Pyridyl, X = O, S), and Their Intra- and Intermolecular Ligand Exchange in Solution
by Anne Seidel, Mareike Weigel, Lisa Ehrlich, Robert Gericke, Erica Brendler and Jörg Wagler
Crystals 2022, 12(8), 1054; https://doi.org/10.3390/cryst12081054 - 28 Jul 2022
Cited by 4 | Viewed by 1556
Abstract
A series of pyridine-2-olates (pyO) and pyridine-2-thiolates (pyS) of silicon was studied in solid state and in solution. The crystal structures of Me3Si(pyO) (1a), Me3Si(pyS) (1b), Me2Si(pyO)2 (2a), Me2 [...] Read more.
A series of pyridine-2-olates (pyO) and pyridine-2-thiolates (pyS) of silicon was studied in solid state and in solution. The crystal structures of Me3Si(pyO) (1a), Me3Si(pyS) (1b), Me2Si(pyO)2 (2a), Me2Si(pyS)2 (2b), Ph2Si(pyO)2 (3a) and Ph2Si(pyS)2 (3b) were determined by X-ray diffraction. For that purpose, crystals of the (at room temperature) liquid compounds 1a and 1b were grown in a capillary on the diffractometer. Compounds 1a, 1b, 2a, 2b and 3a feature tetracoordinate silicon atoms in the solid state, whereas 3b gave rise to a series of four crystal structures in which the Si atoms of this compound are hexacoordinate. Two isomers (3b1 with all-cis arrangement of the C2N2S2 donor atoms in P1¯, and 3b2 with trans S-Si-S axis in P21/n) formed individual crystal batches, which allowed for their individual 29Si NMR spectroscopic study in the solid state (the determination of their chemical shift anisotropy tensors). Furthermore, the structures of a less stable modification of 3b2 (in C2/c) as well as a toluene solvate 3b2 (toluene) (in P1¯) were determined. In CDCl3, the equimolar solutions of the corresponding pairs of pyO and pyS compounds (2a/2b and 3a/3b) showed substituent scrambling with the formation of the products Me2Si(pyO)(pyS) (2c) and Ph2Si(pyO)(pyS) (3c), respectively, as minor components in the respective substituent exchange equilibrium. Full article
(This article belongs to the Special Issue Multifunctional Coordination Polymers: Synthesis, Structure, Properties and Applications)
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Review

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16 pages, 3772 KiB  
Review
Biomedical Applications of Titanium Alloys Modified with MOFs—Current Knowledge and Further Development Directions
by Marcel Jakubowski, Aleksandra Domke, Adam Voelkel and Mariusz Sandomierski
Crystals 2023, 13(2), 257; https://doi.org/10.3390/cryst13020257 - 02 Feb 2023
Cited by 4 | Viewed by 1660
Abstract
MOFs (Metal–Organic Frameworks) are so-called coordination polymers with a porous crystalline structure. In this review, the main emphasis was placed on these compounds’ use in modifying titanium implants. The article describes what MOFs are, gives examples of ligands used in the synthesis of [...] Read more.
MOFs (Metal–Organic Frameworks) are so-called coordination polymers with a porous crystalline structure. In this review, the main emphasis was placed on these compounds’ use in modifying titanium implants. The article describes what MOFs are, gives examples of ligands used in the synthesis of MOFs, and describes a subgroup of these materials, i.e., Zeolitic imidazolate frameworks. The article also lists the basic biomedical applications of these compounds. This review shows the significant impact of titanium surface modification with Metal–Organic Frameworks. These modifications make it possible to obtain layers with antibacterial properties, better corrosion resistance, increasing cell proliferation, faster bone growth in vivo, and much more. The presented work shows that the modification of titanium with MOFs is a very promising method of improving their properties. We hope that the prepared review will help research groups from around the world in the preparation of implants modified with Metal–Organic Frameworks with enhanced properties and utility applications. Full article
(This article belongs to the Special Issue Multifunctional Coordination Polymers: Synthesis, Structure, Properties and Applications)
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