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Coordination Polymers: Synthesis, Structure, Luminescence and/or Magnetic Properties

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: closed (30 June 2021) | Viewed by 14810

Special Issue Editor


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Guest Editor
N.S. Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Leninsky Prosp. 31, 119991 Moscow, Russia
Interests: coordination chemistry; secondary building blocks; single-crystal X-ray diffraction; magnetic properties; photoluminescence
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Special Issue Information

Dear Colleagues, 

As the Guest Editor of a Special Issue of Molecules on "Coordination Polymers: Synthesis, Structure, Luminescence and/or Magnetic Properties", it is my pleasure to invite you to submit an article on this topic. This Issue is devoted to the design of new coordination polymers (including porous compounds), the study of metal- or ligand-centered luminescence and/or magnetic properties, as well as the influence of different substrates on their absorption. The article may be either a full paper or a communication based on your own research in this broad area of coordination chemistry, or may be a focused review article on some aspect of the subject. All submissions will be subject to peer review.

Prof. Dr. Mikhail A. Kiskin
Guest Editor

Manuscript Submission Information

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Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 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
  • synthesis
  • structure
  • magnetic properties
  • photoluminescence
  • switchable properties
  • application

Published Papers (6 papers)

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Research

10 pages, 4335 KiB  
Article
Synthesis, Crystal Structure, and Luminescence of Cadmium(II) and Silver(I) Coordination Polymers Based on 1,3-Bis(1,2,4-triazol-1-yl)adamantane
by Roman D. Marchenko, Taisiya S. Sukhikh, Alexey A. Ryadun and Andrei S. Potapov
Molecules 2021, 26(17), 5400; https://doi.org/10.3390/molecules26175400 - 05 Sep 2021
Cited by 6 | Viewed by 2237
Abstract
Coordination polymers with a new rigid ligand 1,3-bis(1,2,4-triazol-1-yl)adamantane (L) were prepared by its reaction with cadmium(II) or silver(I) nitrates. Crystal structure of the coordination polymers was determined using single-crystal X-ray diffraction analysis. Silver formed two-dimensional coordination polymer [Ag(L)NO3]n, in [...] Read more.
Coordination polymers with a new rigid ligand 1,3-bis(1,2,4-triazol-1-yl)adamantane (L) were prepared by its reaction with cadmium(II) or silver(I) nitrates. Crystal structure of the coordination polymers was determined using single-crystal X-ray diffraction analysis. Silver formed two-dimensional coordination polymer [Ag(L)NO3]n, in which metal ions are linked by 1,3-bis(1,2,4-triazol-1-yl)adamantane ligands, coordinated by nitrogen atoms at positions 2 and 4 of 1,2,4-triazole rings. Layers of the coordination polymer consist of rare 18- and 30-membered {Ag2L2} and {Ag4L4} metallocycles. Cadmium(II) nitrate formed two kinds of one-dimensional coordination polymers depending on the metal-to-ligand ratio used in the synthesis. Coordination polymer [Cd(L)2(NO3)2]n was obtained in case of a 1:2 M:L ratio, while for M:L = 2:1 product {[Cd(L)(NO3)2(CH3OH)]·0.5CH3OH}n was isolated. All coordination polymers demonstrated ligand-centered emission near 450 nm upon excitation at 370 nm. Full article
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22 pages, 5336 KiB  
Article
Cadmium-Inspired Self-Polymerization of {LnIIICd2} Units: Structure, Magnetic and Photoluminescent Properties of Novel Trimethylacetate 1D-Polymers (Ln = Sm, Eu, Tb, Dy, Ho, Er, Yb)
by Maxim A. Shmelev, Ruslan A. Polunin, Natalia V. Gogoleva, Igor S. Evstifeev, Pavel N. Vasilyev, Alexey A. Dmitriev, Evgenia A. Varaksina, Nikolay N. Efimov, Ilya V. Taydakov, Aleksey A. Sidorov, Mikhail A. Kiskin, Nina P. Gritsan, Sergey V. Kolotilov and Igor L. Eremenko
Molecules 2021, 26(14), 4296; https://doi.org/10.3390/molecules26144296 - 15 Jul 2021
Cited by 9 | Viewed by 1938
Abstract
A series of heterometallic carboxylate 1D polymers of the general formula [LnIIICd2(piv)7(H2O)2]n·nMeCN (LnIII = Sm (1), Eu (2), Tb (3), Dy (4), [...] Read more.
A series of heterometallic carboxylate 1D polymers of the general formula [LnIIICd2(piv)7(H2O)2]n·nMeCN (LnIII = Sm (1), Eu (2), Tb (3), Dy (4), Ho (5), Er (6), Yb (7); piv = anion of trimethylacetic acid) was synthesized and structurally characterized. The use of CdII instead of ZnII under similar synthetic conditions resulted in the formation of 1D polymers, in contrast to molecular trinuclear complexes with LnIIIZn2 cores. All complexes 17 are isostructural. The luminescent emission and excitation spectra for 24 have been studied, the luminescence decay kinetics for 2 and 3 was measured. Magnetic properties of the complexes 35 and 7 have been studied; 4 and 7 exhibited the properties of field-induced single-molecule magnets in an applied external magnetic field. Magnetic properties of 4 and 7 were modelled using results of SA-CASSCF/SO-RASSI calculations and SINGLE_ANISO procedure. Based on the analysis of the magnetization relaxation and the results of ab initio calculations, it was found that relaxation in 4 predominantly occurred by the sum of the Raman and QTM mechanisms, and by the sum of the direct and Raman mechanisms in the case of 7. Full article
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13 pages, 3326 KiB  
Article
A Highly Selective Turn-On Fluorescent Probe for the Detection of Zinc
by Ling-Yi Shen, Xiao-Li Chen, Xian-Jiong Yang, Hong Xu, Ya-Li Huang, Xing Zhang, Carl Redshaw and Qi-Long Zhang
Molecules 2021, 26(13), 3825; https://doi.org/10.3390/molecules26133825 - 23 Jun 2021
Cited by 18 | Viewed by 2445
Abstract
A novel turn-on fluorescence probe L has been designed that exhibits high selectivity and sensitivity with a detection limit of 9.53 × 10−8 mol/L for the quantification of Zn2+. 1H-NMR spectroscopy and single crystal X-ray diffraction analysis revealed the [...] Read more.
A novel turn-on fluorescence probe L has been designed that exhibits high selectivity and sensitivity with a detection limit of 9.53 × 10−8 mol/L for the quantification of Zn2+. 1H-NMR spectroscopy and single crystal X-ray diffraction analysis revealed the unsymmetrical nature of the structure of the Schiff base probe L. An emission titration experiment in the presence of different molar fractions of Zn2+ was used to perform a Job’s plot analysis. The results showed that the stoichiometric ratio of the complex formed by L and Zn2+ was 1:1. Moreover, the molecular structure of the mononuclear Cu complex reveals one ligand L coordinates with one Cu atom in the asymmetric unit. On adding CuCl2 to the ZnCl2/L system, a Cu-Zn complex was formed and a strong quenching behavior was observed, which inferred that the Cu2+ displaced Zn2+ to coordinate with the imine nitrogen atoms and hydroxyl oxygen atoms of probe L. Full article
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16 pages, 5015 KiB  
Article
Heteroleptic LaIII Anilate/Dicarboxylate Based Neutral 3D-Coordination Polymers
by Olesya Y. Trofimova, Arina V. Maleeva, Irina V. Ershova, Anton V. Cherkasov, Georgy K. Fukin, Rinat R. Aysin, Konstantin A. Kovalenko and Alexandr V. Piskunov
Molecules 2021, 26(9), 2486; https://doi.org/10.3390/molecules26092486 - 24 Apr 2021
Cited by 9 | Viewed by 1884
Abstract
Three new 3D metal–organic frameworks of lanthanum based on mixed anionic ligands, [(La2(pQ)2(BDC)4)·4DMF]n, [(La2(pQ)2(DHBDC)4)·4DMF]n, [(La2(CA)2(BDC)4)·4DMF]n (pQ—dianion of 2,5-dihydroxy-3,6-di-tert-butyl-para-quinone, CA—dianion of [...] Read more.
Three new 3D metal–organic frameworks of lanthanum based on mixed anionic ligands, [(La2(pQ)2(BDC)4)·4DMF]n, [(La2(pQ)2(DHBDC)4)·4DMF]n, [(La2(CA)2(BDC)4)·4DMF]n (pQ—dianion of 2,5-dihydroxy-3,6-di-tert-butyl-para-quinone, CA—dianion of chloranilic acid, BDC-1,4-benzenedicarboxylate, DHBDC-2,5-dihydroxy-1,4-benzenedicarboxylate and DMF-N,N′-dimethylformamide), were synthesized using solvothermal methodology. Coordination polymers demonstrate the rare xah or 4,6T187 topology of a 3D framework. The homoleptic 2D-coordination polymer [(La2(pQ)3)·4DMF]n was obtained as a by-product in the course of synthetic procedure optimization. The thermal stability, spectral characteristics and porosity of coordination polymers were investigated. Full article
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15 pages, 3394 KiB  
Article
3D Metal–Organic Frameworks Based on Co(II) and Bithiophendicarboxylate: Synthesis, Crystal Structures, Gas Adsorption, and Magnetic Properties
by Vadim A. Dubskikh, Anna A. Lysova, Denis G. Samsonenko, Alexander N. Lavrov, Konstantin A. Kovalenko, Danil N. Dybtsev and Vladimir P. Fedin
Molecules 2021, 26(5), 1269; https://doi.org/10.3390/molecules26051269 - 26 Feb 2021
Cited by 16 | Viewed by 2413
Abstract
Three new 3D metal-organic porous frameworks based on Co(II) and 2,2′-bithiophen-5,5′-dicarboxylate (btdc2−) [Co3(btdc)3(bpy)2]·4DMF, 1; [Co3(btdc)3(pz)(dmf)2]·4DMF·1.5H2O, 2; [Co3(btdc)3(dmf)4]∙2DMF∙2H2O, [...] Read more.
Three new 3D metal-organic porous frameworks based on Co(II) and 2,2′-bithiophen-5,5′-dicarboxylate (btdc2−) [Co3(btdc)3(bpy)2]·4DMF, 1; [Co3(btdc)3(pz)(dmf)2]·4DMF·1.5H2O, 2; [Co3(btdc)3(dmf)4]∙2DMF∙2H2O, 3 (bpy = 2,2′-bipyridyl, pz = pyrazine, dmf = N,N-dimethylformamide) were synthesized and structurally characterized. All compounds share the same trinuclear carboxylate building units {Co3(RCOO)6}, connected either by btdc2– ligands (1, 3) or by both btdc2– and pz bridging ligands (2). The permanent porosity of 1 was confirmed by N2, O2, CO, CO2, CH4 adsorption measurements at various temperatures (77 K, 273 K, 298 K), resulted in BET surface area 667 m2⋅g−1 and promising gas separation performance with selectivity factors up to 35.7 for CO2/N2, 45.4 for CO2/O2, 20.8 for CO2/CO, and 4.8 for CO2/CH4. The molar magnetic susceptibilities χp(T) were measured for 1 and 2 in the temperature range 1.77–330 K at magnetic fields up to 10 kOe. The room-temperature values of the effective magnetic moments for compounds 1 and 2 are μeff (300 K) ≈ 4.93 μB. The obtained results confirm the mainly paramagnetic nature of both compounds with some antiferromagnetic interactions at low-temperatures T < 20 K in 2 between the Co(II) cations separated by short pz linkers. Similar conclusions were also derived from the field-depending magnetization data of 1 and 2. Full article
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9 pages, 1743 KiB  
Article
Microwave-Assisted Synthesis, Characterization and Modeling of CPO-27-Mg Metal-Organic Framework for Drug Delivery
by Anton I. Kudelin, Konstantinos Papathanasiou, Vera Isaeva, Juergen Caro, Tapio Salmi and Leonid M. Kustov
Molecules 2021, 26(2), 426; https://doi.org/10.3390/molecules26020426 - 15 Jan 2021
Cited by 4 | Viewed by 3104
Abstract
The coordination polymer CPO-27-Mg was rapidly synthesized under microwave irradiation. This material exhibits a sufficiently high drug loading towards aspirin (~8% wt.) and paracetamol (~14% wt.). The binding of these two molecules with the inner surface of the metal-organic framework was studied employing [...] Read more.
The coordination polymer CPO-27-Mg was rapidly synthesized under microwave irradiation. This material exhibits a sufficiently high drug loading towards aspirin (~8% wt.) and paracetamol (~14% wt.). The binding of these two molecules with the inner surface of the metal-organic framework was studied employing the Gaussian and Plane Wave approach of the Density Functional Theory. The structure of CPO-27-Mg persists after the adsorption of aspirin or paracetamol and their desorption energies, being quite high, decrease under solvent conditions. Full article
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