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Special Issue "Functional Magnetic Molecular Materials"

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

Deadline for manuscript submissions: 31 December 2020.

Special Issue Editors

Dr. Dawid Pinkowicz
Website
Guest Editor
Uniwersytet Jagielloński w Krakowie, Wydział Chemii, Gronostajowa 2, 30-387 Kraków, Poland
Interests: molecular magnetism; molecular materials; multifunctional materials; photomagnets; magneto-optics; quantum nanomagnets; magnetic sponge systems; spin crossover systems; organic radicals; secondary building blocks; molecular modules; single-crystal-to-single-crystal transformations; molecular recognition; supramolecular architectures; magneto–structural correlations under pressure
Dr. Robert Podgajny
Website
Guest Editor
Uniwersytet Jagielloński w Krakowie, Wydział Chemii, Gronostajowa 2, 30-387 Kraków, Poland
Interests: molecular magnetism; molecular materials; multifunctional materials; photomagnets; magneto-optics; quantum nanomagnets; magnetic sponge systems; spin crossover systems; organic radicals; secondary building blocks; molecular modules; single-crystal-to-single-crystal transformations; molecular recognition; supramolecular architectures; magneto–structural correlations under pressure

Special Issue Information

Dear Colleagues,

Functional magnetic molecular materials constitute a special class of "smart compounds" that combine various physical and chemical properties like porosity, gas/solvent sorption, electrical conductivity, ferroelectricity, redox activity, chirality, luminescence, and other optical properties with magnetism. Such combinations can lead to desirable switching/sensing behaviour and memory effects, which are necessary prerequisites for the construction of molecular devices. The field of functional magnetic molecular materials is under constant development, and new fascinating compounds are reported every day, leading to new discoveries and examples of strong coupling between magnetic properties and other functionalities.

The design and construction of functional magnetic molecular materials requires the close collaboration of chemists, theoreticians, physicists, and materials scientists. Moreover, a suitable communication platform is also necessary. The following Special Issue of Molecules is inteded to provide a useful forum for the dissemination of the most relevant and important findings in this vein, along with review contributions that summarize the recent developments in magnetic coordination polymers and MOFs, single molecule and single chain magnets, spin crossover materials, chiral magnets, ferroelectrics, multiferroics, and photomagnets.

Dr. Dawid Pinkowicz
Dr. Robert Podgajny
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 papers will be 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. Molecules is an international peer-reviewed open access semimonthly 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 2000 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

  • Transition metal chemistry
  • Lanthanides and actinides
  • Multifunctionality
  • Magnetism
  • Nanomagnets
  • Ferromagnets
  • Bottom-up approach
  • Crystal engineering
  • Photo-switching
  • Molecular magnetism
  • Spin crossover materials
  • Magnetic coordination materials.

Published Papers (6 papers)

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Research

Open AccessFeature PaperArticle
First Cobalt(II) Spin Crossover Compound with N4S2-Donorset
Molecules 2020, 25(4), 855; https://doi.org/10.3390/molecules25040855 - 14 Feb 2020
Cited by 1
Abstract
Herein we report the synthesis and characterization of a novel bis-tridentate 1,3,4-thiadiazole ligand (L = 2,5-bis[(2-pyridylmethyl)thio]methyl-1,3,4-thiadiazole). Two new mononuclear complexes of the type [MII(L)2](ClO4)2 (with M = FeII (C1) and [...] Read more.
Herein we report the synthesis and characterization of a novel bis-tridentate 1,3,4-thiadiazole ligand (L = 2,5-bis[(2-pyridylmethyl)thio]methyl-1,3,4-thiadiazole). Two new mononuclear complexes of the type [MII(L)2](ClO4)2 (with M = FeII (C1) and CoII (C2)) have been synthesized, containing the new ligand (L). In both complexes the metal centers are coordinated by an N4S2-donorset and each of the two ligands is donating to the metal ion with just one of the tridentate pockets. The iron(II) complex (C1) is in the low spin [LS] state below room temperature and shows an increase in the magnetic moment only above 300 K. In contrast, the cobalt(II) complex (C2) shows a gradual spin crossover (SCO) with T1/2 = 175 K. To our knowledge, this is the first cobalt(II) SCO complex with an N4S2-coordination. Full article
(This article belongs to the Special Issue Functional Magnetic Molecular Materials)
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Open AccessArticle
Iron(II) Spin Crossover Complexes with 4,4′-Dipyridylethyne—Crystal Structures and Spin Crossover with Hysteresis
Molecules 2020, 25(3), 581; https://doi.org/10.3390/molecules25030581 - 29 Jan 2020
Cited by 1
Abstract
Three new iron(II) 1D coordination polymers with cooperative spin crossover behavior showing thermal hysteresis loops were synthesized using N2O2 Schiff base-like equatorial ligands and 4,4′-dipyridylethyne as a bridging, rigid axial linker. One of those iron(II) 1D coordination polymers showed a [...] Read more.
Three new iron(II) 1D coordination polymers with cooperative spin crossover behavior showing thermal hysteresis loops were synthesized using N2O2 Schiff base-like equatorial ligands and 4,4′-dipyridylethyne as a bridging, rigid axial linker. One of those iron(II) 1D coordination polymers showed a 73 K wide hysteresis below room temperature, which, upon solvent loss, decreased to a still remarkable 30 K wide hysteresis. Single crystal X-ray structures of two iron(II) coordination polymers and T-dependent powder XRD patterns are discussed to obtain insight into the structure property relationship of those materials. Full article
(This article belongs to the Special Issue Functional Magnetic Molecular Materials)
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Open AccessArticle
Redox-Modulations of Photophysical and Single-molecule Magnet Properties in Ytterbium Complexes Involving Extended-TTF Triads
Molecules 2020, 25(3), 492; https://doi.org/10.3390/molecules25030492 - 23 Jan 2020
Cited by 3
Abstract
The reaction between the 2,2’-benzene-1,4-diylbis(6-hydroxy-4,7-di-tert-butyl-1,3-benzodithiol-2-ylium-5-olate triad (H2SQ) and the metallo-precursor [Yb(hfac)3]⋅2H2O led to the formation of a dinuclear coordination complex of formula [Yb2(hfac)6(H2SQ)]⋅0.5CH2Cl [...] Read more.
The reaction between the 2,2’-benzene-1,4-diylbis(6-hydroxy-4,7-di-tert-butyl-1,3-benzodithiol-2-ylium-5-olate triad (H2SQ) and the metallo-precursor [Yb(hfac)3]⋅2H2O led to the formation of a dinuclear coordination complex of formula [Yb2(hfac)6(H2SQ)]⋅0.5CH2Cl2 (H2SQ-Yb). After chemical oxidation of H2SQ in 2,2’-cyclohexa-2,5-diene-1,4-diylidenebis(4,7-di-tert-butyl-1,3-benzodithiole-5,6-dione (Q), the latter triad reacted with the [Yb(hfac)3]⋅2H2O precursor to give the dinuclear complex of formula [Yb2(hfac)6(Q)] (Q-Yb). Both dinuclear compounds have been characterized by X-ray diffraction, DFT optimized structure and electronic absorption spectra. They behaved as field-induced Single-Molecule Magnets (SMMs) nevertheless the chemical oxidation of the semiquinone to quinone moieties accelerated by a factor of five the relaxation time of the magnetization of Q-Yb compared to the one for H2SQ-Yb. The H2SQ triad efficiently sensitized the YbIII luminescence while the chemical oxidation of H2SQ into Q induced strong modification of the absorption properties and thus a quenching of the YbIII luminescence for Q-Yb. In other words, both magnetic modulation and luminescence quenching are reached by the oxidation of the protonated semiquinone into quinone. Full article
(This article belongs to the Special Issue Functional Magnetic Molecular Materials)
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Open AccessArticle
The Structural and Magnetic Properties of FeII and CoII Complexes with 2-(furan-2-yl)-5-pyridin-2-yl-1,3,4-oxadiazole
Molecules 2020, 25(2), 277; https://doi.org/10.3390/molecules25020277 - 09 Jan 2020
Cited by 2
Abstract
Two novel coordination compounds containing heterocyclic bidentate N,N-donor ligand 2-(furan-2-yl)-5-(pyridin-2-yl)-1,3,4-oxadiazole (fpo) were synthesized. A general formula for compounds originating from perchlorates of iron, cobalt, and fpo can be written as: [M(fpo)2(H2O)2](ClO4)2 [...] Read more.
Two novel coordination compounds containing heterocyclic bidentate N,N-donor ligand 2-(furan-2-yl)-5-(pyridin-2-yl)-1,3,4-oxadiazole (fpo) were synthesized. A general formula for compounds originating from perchlorates of iron, cobalt, and fpo can be written as: [M(fpo)2(H2O)2](ClO4)2 (M = Fe(II) for (1) Co(II) for (2)). The characterization of compounds was performed by general physico-chemical methods—elemental analysis (EA), Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR) in case of organics, and single crystal X-ray diffraction (sXRD). Moreover, magneto-chemical properties were studied employing measurements in static field (DC) for 1 and X-band EPR (Electron paramagnetic resonance), direct current (DC), and alternating current (AC) magnetic measurements in case of 2. The analysis of DC magnetic properties revealed a high spin arrangement in 1, significant rhombicity for both complexes, and large magnetic anisotropy in 2 (D = −21.2 cm−1). Moreover, 2 showed field-induced slow relaxation of the magnetization (Ueff = 65.3 K). EPR spectroscopy and ab initio calculations (CASSCF/NEVPT2) confirmed the presence of easy axis anisotropy and the importance of the second coordination sphere. Full article
(This article belongs to the Special Issue Functional Magnetic Molecular Materials)
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Open AccessArticle
Structural Disorder in High-Spin {CoII9WV6} (Core)-[Pyridine N-Oxides] (Shell) Architectures
Molecules 2020, 25(2), 251; https://doi.org/10.3390/molecules25020251 - 08 Jan 2020
Cited by 1
Abstract
The combinations of Co(II), octacyanidotungstate(V), and monodentate pyridine N-oxide (pyNO) or 4-phenylpyridine N-oxide (4-phpyNO) led to crystallization of novel crystalline phases {CoII[CoII8(pyNO)12(MeOH)12][WV(CN)8]6} (1) and [...] Read more.
The combinations of Co(II), octacyanidotungstate(V), and monodentate pyridine N-oxide (pyNO) or 4-phenylpyridine N-oxide (4-phpyNO) led to crystallization of novel crystalline phases {CoII[CoII8(pyNO)12(MeOH)12][WV(CN)8]6} (1) and {CoII[CoII8(4-phpyNO)7(MeOH)17][WV(CN)8]6}·7MeOH·(4-phpyNO)3 (2). In both architectures, metal–cyanide clusters are coordinated by N-oxide ligands in a simple monodentate manner to give the spherical objects of over 1 nm core diameter and about 2.2 nm (1) and 3 nm (2) of the total diameter, terminated with the aromatic rings. The supramolecular architecture is dominated by dense and rich π–π interaction systems. Both structures are characterized by a significant structural disorder in ligand shell, described with the suitable probability models. For 1, the π–π interactions between the pyNO ligands attached to the same metal centers are suggested for the first time. In 2, 4-phpyNO acts as monodentate ligand and as the crystallization molecule. Magnetic studies indicate the high-spin ground state due to the ferromagnetic interactions Co(II)–W(V) through the cyanido bridges. Due to the high symmetry of the clusters, no signature of slow magnetic relaxation was observed. The characterization is completed by solid-state IR and UV–Vis–NIR spectroscopy. The conditions for the stable M9M’6-based crystals formation are synthetically discussed in terms of the type of capping ligands: monodentate, bridging, and chelating. The potential of the related polynuclear forms toward the magnetism-based functional properties is critically indicated. Full article
(This article belongs to the Special Issue Functional Magnetic Molecular Materials)
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Open AccessFeature PaperArticle
Mapping Magnetic Properties and Relaxation in Vanadium(IV) Complexes with Lanthanides by Electron Paramagnetic Resonance
Molecules 2019, 24(24), 4582; https://doi.org/10.3390/molecules24244582 - 14 Dec 2019
Abstract
Vanadium(IV) complexes are actively studied as potential candidates for molecular spin qubits operating at room temperatures. They have longer electron spin decoherence times than many other transition ions, being the key property for applications in quantum information processing. In most cases reported to [...] Read more.
Vanadium(IV) complexes are actively studied as potential candidates for molecular spin qubits operating at room temperatures. They have longer electron spin decoherence times than many other transition ions, being the key property for applications in quantum information processing. In most cases reported to date, the molecular complexes were optimized through the design for this purpose. In this work, we investigate the relaxation properties of vanadium(IV) ions incorporated in complexes with lanthanides using electron paramagnetic resonance (EPR). In all cases, the VO6 moieties with no nuclear spins in the first coordination sphere are addressed. We develop and implement the approaches for facile diagnostics of relaxation characteristics in individual VO6 moieties of such compounds. Remarkably, the estimated relaxation times are found to be close to those of other vanadium-based qubits obtained previously. In the future, a synergistic combination of qubit-friendly properties of vanadium ions with single-molecule magnetism and luminescence of lanthanides can be pursued to realize new functionalities of such materials. Full article
(This article belongs to the Special Issue Functional Magnetic Molecular Materials)
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