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Magnetochemistry
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Stimuli-Responsive Magnetic Molecular Materials
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Stimuli-Responsive Magnetic Molecular Materials

A special issue of Magnetochemistry (ISSN 2312-7481). This special issue belongs to the section "Magnetic Materials".

Deadline for manuscript submissions: closed (30 June 2021) | Viewed by 24512

Special Issue Editors

Prof. Dr. Boris Tsukerblat

E-Mail Website
Guest Editor
Department of Chemistry, Ben-Gurion University of the Negev, Beer Sheba, Winnipeg MB R3P 0N5, Israel
Interests: molecular magnetism and molecule-based magnetic materials; cooperative phenomena in molecule based magnets; vibronic interactions and Jahn-Teller effect in molecules and crystals, optical materials; Computational and symmetry assisted approaches in theoretical chemistry
Prof. Dr. Andrew Palii

E-Mail Website
Guest Editor
Institute of Problems of Chemical Physics, 142432 Chernogolovka, Moscow Region, Russia
Interests: molecular magnets; spintronics; quantum spin processing; nanomagnets; metal–organic ferromagnets; cage automats
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear colleagues,

This Special Issue aims to provide a valuable forum where scientists in different fields will be able to share their most recent novel findings on the control and manipulation of physically and practically important properties of molecule-based materials.

Topics to be covered include but are not limited to:

  • Molecule-based magnets: magnetoelectric effect, electric field control of spin states and magnetic exchange coupling in molecule-based magnetic materials, mixed valence systems, etc., in spin communication;
  • Temperature- and pressure-induced spin-crossover (SCO) phenomenon, valent tautomerism, light-induced excited spin state trapping (LIESST);
  • Light-responsive magnetic molecules: single-molecule magnets, single-chain magnets, and chiral magnets, optical switching at molecular level and photoinduced charge transfer;
  • Photoswitching, photomagnetic effect, photomagnetic chromophores, photoinduced charge transfer, light-induced changes in spin state and structure;
  • Applications of stimuli-responsive magnetic molecular materials in molecular electronics, spintronics, and quantum computing;
  • Stimuli-responsive magnetic particles in biomedical applications.

Prof. Dr. Boris Tsukerblat
Prof. Dr. Andrew Palii
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. Magnetochemistry 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 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.

Published Papers (9 papers)

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Research

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14 pages, 3394 KiB  
Article
Pyridyl-Thioethers as Capping Ligands for the Design of Heteroleptic Fe(II) Complexes with Spin-Crossover Behavior
by Ökten Üngör, Dilyara Igimbayeva, Alina Dragulescu-Andrasi, Sandugash Yergeshbayeva, Teresa Delgado, Samuel M. Greer, Gabrielle Donalson, Minyoung Jo, Rakhmetulla Erkasov and Michael Shatruk
Magnetochemistry 2021, 7(10), 134; https://0-doi-org.brum.beds.ac.uk/10.3390/magnetochemistry7100134 - 01 Oct 2021
Cited by 2 | Viewed by 1827
Abstract
Mononuclear heteroleptic complexes [Fe(tpma)(bimz)](ClO4)2 (1a), [Fe(tpma)(bimz)](BF4)2 (1b), [Fe(bpte)(bimz)](ClO4)2 (2a), and [Fe(bpte)(bimz)](BF4)2 (2b) (tpma = tris(2-pyridylmethyl)amine, bpte = S,S′-bis(2-pyridylmethyl)-1,2-thioethane, bimz = 2,2′-biimidazoline) were [...] Read more.
Mononuclear heteroleptic complexes [Fe(tpma)(bimz)](ClO4)2 (1a), [Fe(tpma)(bimz)](BF4)2 (1b), [Fe(bpte)(bimz)](ClO4)2 (2a), and [Fe(bpte)(bimz)](BF4)2 (2b) (tpma = tris(2-pyridylmethyl)amine, bpte = S,S′-bis(2-pyridylmethyl)-1,2-thioethane, bimz = 2,2′-biimidazoline) were prepared by reacting the corresponding Fe(II) salts with stoichiometric amounts of the ligands. All complexes exhibit temperature-induced spin crossover (SCO), but the SCO temperature is substantially lower for complexes 1a and 1b as compared to 2a and 2b, indicating the stronger ligand field afforded by the N2S2-coordinating bpte ligand relative to the N4-coordinating tpma. Our findings suggest that ligands with mixed N/S coordination can be employed to discover new SCO complexes and to tune the transition temperature of known SCO compounds by substituting for purely N-coordinating ligands. Full article
(This article belongs to the Special Issue Stimuli-Responsive Magnetic Molecular Materials)
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15 pages, 2340 KiB  
Article
Self-Assembly and Magnetic Order of Bi-Molecular 2D Spin Lattices of M(II,III) Phthalocyanines on Au(111)
by Miloš Baljozović, Xunshan Liu, Olha Popova, Jan Girovsky, Jan Nowakowski, Harald Rossmann, Thomas Nijs, Mina Moradi, S. Fatemeh Mousavi, Nicholas C. Plumb, Milan Radović, Nirmalya Ballav, Jan Dreiser, Silvio Decurtins, Igor A. Pašti, Natalia V. Skorodumova, Shi-Xia Liu and Thomas A. Jung
Magnetochemistry 2021, 7(8), 119; https://0-doi-org.brum.beds.ac.uk/10.3390/magnetochemistry7080119 - 19 Aug 2021
Cited by 4 | Viewed by 3377
Abstract
Single layer low-dimensional materials are presently of emerging interest, including in the context of magnetism. In the present report, on-surface supramolecular architecturing was further developed and employed to create surface supported two-dimensional binary spin arrays on atomically clean non-magnetic Au(111). By chemical programming [...] Read more.
Single layer low-dimensional materials are presently of emerging interest, including in the context of magnetism. In the present report, on-surface supramolecular architecturing was further developed and employed to create surface supported two-dimensional binary spin arrays on atomically clean non-magnetic Au(111). By chemical programming of the modules, different checkerboards were produced combining phthalocyanines containing metals of different oxidation and spin states, diamagnetic zinc, and a metal-free ‘spacer’. In an in-depth, spectro-microscopy and theoretical account, we correlate the structure and the magnetic properties of these tunable systems and discuss the emergence of 2D Kondo magnetism from the spin-bearing components and via the physico-chemical bonding to the underlying substrate. The contributions of the individual elements, as well as the role of the electronic surface state in the bottom substrate, are discussed, also looking towards further in-depth investigations. Full article
(This article belongs to the Special Issue Stimuli-Responsive Magnetic Molecular Materials)
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11 pages, 2872 KiB  
Article
Magnetoelectricity in Jahn–Teller Elastics
by Michael Kaplan
Magnetochemistry 2021, 7(7), 95; https://0-doi-org.brum.beds.ac.uk/10.3390/magnetochemistry7070095 - 29 Jun 2021
Viewed by 1457
Abstract
The magnetoelectric effects in Jahn–Teller crystals are discussed on the basis of phenomenology and microscopic theory. New magnetoelectric effects—metamagnetoelectricity—are analyzed. Formation of multiferroic crystal states as the consequence of the cooperative Jahn–Teller effect is discussed. Full article
(This article belongs to the Special Issue Stimuli-Responsive Magnetic Molecular Materials)
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31 pages, 10509 KiB  
Article
Reciprocating Thermal Behavior in Multichannel Relaxation of Cobalt(II) Based Single Ion Magnets
by Cyril Rajnák, Ján Titiš and Roman Boča
Magnetochemistry 2021, 7(6), 76; https://0-doi-org.brum.beds.ac.uk/10.3390/magnetochemistry7060076 - 25 May 2021
Cited by 12 | Viewed by 2425
Abstract
A series of mononuclear Co(II) complexes showing slow magnetic relaxation is assessed from the point of view of relaxation mechanisms. In certain cases, the reciprocating thermal behavior is detected: On cooling, the slow relaxation time is prolonged until a certain limit and then, [...] Read more.
A series of mononuclear Co(II) complexes showing slow magnetic relaxation is assessed from the point of view of relaxation mechanisms. In certain cases, the reciprocating thermal behavior is detected: On cooling, the slow relaxation time is prolonged until a certain limit and then, unexpectedly, is accelerated. The low-temperature magnetic data can be successfully fitted by assuming Raman and/or phonon bottleneck mechanisms of the slow magnetic relaxation for the high-frequency relaxation channel. An additional term with the negative temperature exponent is capable of reproducing the whole experimental dataset. Full article
(This article belongs to the Special Issue Stimuli-Responsive Magnetic Molecular Materials)
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11 pages, 585 KiB  
Article
Role of Surface Effects in the Vibrational Density of States and the Vibrational Entropy in Spin Crossover Nanomaterials: A Molecular Dynamics Investigation
by Alaa Fahs, William Nicolazzi, Gábor Molnár and Azzedine Bousseksou
Magnetochemistry 2021, 7(2), 27; https://0-doi-org.brum.beds.ac.uk/10.3390/magnetochemistry7020027 - 18 Feb 2021
Cited by 4 | Viewed by 4210
Abstract
Size reduction effects on the lattice dynamics of spin crossover (SCO) thin films have been investigated through molecular dynamics (MD) simulations of the density of vibrational states. The proposed simple model structure and reduced force field allows us to obtain good orders of [...] Read more.
Size reduction effects on the lattice dynamics of spin crossover (SCO) thin films have been investigated through molecular dynamics (MD) simulations of the density of vibrational states. The proposed simple model structure and reduced force field allows us to obtain good orders of magnitude of the sound velocity in both spin states and takes into account the contribution of free surfaces in the vibrational properties of very thin films (below a thickness of 12 nm). The slab method issue from the field of surface physico-chemistry has been employed to extract surface thermodynamic quantities. In combination with the related slab-adapted method, the slab approach provides a powerful numerical tool to separate surface contributions from finite-size effects. Due to the relatively low stiffness of SCO materials, the lattice dynamics seems to be governed by surface instead of confinement effects. The size evolution of thermodynamic quantities is successfully reproduced, especially the increase of the vibrational entropy with the size reduction, in good agreement with experimental observations. Full article
(This article belongs to the Special Issue Stimuli-Responsive Magnetic Molecular Materials)
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7 pages, 944 KiB  
Article
Oscillations of EPR Signals Accompanying Belousov–Zhabotinsky Reaction
by Roman Morgunov and Yoshifumi Tanimoto
Magnetochemistry 2021, 7(1), 2; https://0-doi-org.brum.beds.ac.uk/10.3390/magnetochemistry7010002 - 23 Dec 2020
Cited by 1 | Viewed by 2231
Abstract
Periodical transformation of ferroin to ferriin is accompanied by changes in magnetic properties of liquids during Belousov–Zhabotinsky (BZ) reaction malonic acid, sodium bromide, sodium bromate, ferroin, and sulfuric acid. Instead of the earlier studied oscillation of microwave conductivity accompanying an oscillating reaction, we [...] Read more.
Periodical transformation of ferroin to ferriin is accompanied by changes in magnetic properties of liquids during Belousov–Zhabotinsky (BZ) reaction malonic acid, sodium bromide, sodium bromate, ferroin, and sulfuric acid. Instead of the earlier studied oscillation of microwave conductivity accompanying an oscillating reaction, we propose a flash technique to interrupt the BZ reaction by rapid freezing. Rapid cooling of a solution during chemical oscillations results in a frozen system with a fixed concentration of paramagnetic centers Fe3+. EPR spectrum recorded at different stages of the interrupted reaction corresponds to the exact concentration of the ferroin and ferriin components. Following unfreezing unblocks the BZ reaction, and oscillations are still observed. A simulated spectrum allows one to distinguish two groups of Fe3+ ions of different symmetries. The obtained results are important to explain the earlier observed effect of inhomogeneous magnetic field on BZ reaction front velocity. Full article
(This article belongs to the Special Issue Stimuli-Responsive Magnetic Molecular Materials)
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11 pages, 748 KiB  
Article
Interplay of Jahn-Teller Ordering and Spin Crossover in Co(II) Compounds
by Sophia Klokishner and Serghei M. Ostrovsky
Magnetochemistry 2020, 6(4), 62; https://0-doi-org.brum.beds.ac.uk/10.3390/magnetochemistry6040062 - 16 Nov 2020
Cited by 1 | Viewed by 2011
Abstract
The spin crossover phenomena in Co(II) compounds are in the focus of the present paper. A microscopic theoretical approach for the description of spin transitions in mononuclear Co(II) compounds is suggested. Within the framework of this approach there are taken into account two [...] Read more.
The spin crossover phenomena in Co(II) compounds are in the focus of the present paper. A microscopic theoretical approach for the description of spin transitions in mononuclear Co(II) compounds is suggested. Within the framework of this approach there are taken into account two types of interionic interactions that may be operative in the problem such as the electron-deformational interaction and the cooperative Jahn-Teller interaction arising from the coupling of the low-spin state of the Co(II) ion with the tetragonal vibrations of the nearest surrounding. The different role of these interactions in the spin transformation is demonstrated and discussed. On the basis of developed approach a qualitative and quantitative explanation of the experimental data on the temperature dependence of the magnetic susceptibility for the [Co(pyterpy)2](PF6)2, [Co(pyterpy)2](TCNQ)2⋅DMF⋅MeOH and [Co(pyterpy)2](TCNQ)2⋅MeCN⋅MeOH compounds is given. Full article
(This article belongs to the Special Issue Stimuli-Responsive Magnetic Molecular Materials)
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14 pages, 2786 KiB  
Article
Spin Crossover in Bipyridine Derivative Bridged One-Dimensional Iron(III) Coordination Polymer
by Ryuta Ishikawa, Takeshi Noda, Shunya Ueno, Takashi Okubo, Hirofumi Yamakawa, Ken-ichi Sakamoto and Satoshi Kawata
Magnetochemistry 2020, 6(3), 29; https://0-doi-org.brum.beds.ac.uk/10.3390/magnetochemistry6030029 - 01 Jul 2020
Cited by 4 | Viewed by 3198
Abstract
Herein, the syntheses, solid-state molecular structures, and characterization of two types of one-dimensional FeIII coordination polymers showing thermally induced spin crossover are reported. The reaction of [Fe(acen)Cl] (acen2− = N,N′-ethylenebis(acetylacetonylideneaminate) with 3,3′-bpy or 4,4′-bpy (bpy = bipyridine) produced [...] Read more.
Herein, the syntheses, solid-state molecular structures, and characterization of two types of one-dimensional FeIII coordination polymers showing thermally induced spin crossover are reported. The reaction of [Fe(acen)Cl] (acen2− = N,N′-ethylenebis(acetylacetonylideneaminate) with 3,3′-bpy or 4,4′-bpy (bpy = bipyridine) produced zigzag and linear one-dimensional chain complexes, [Fe(acen)(3,3′-bpy)][BPh4] (1) or [NEt3H][Fe(acen)(4,4′-bpy)][BPh4]2·0.5(4,4′-bpy) (2), respectively, as confirmed by single crystal X-ray diffraction analysis. Variable-temperature single crystal X-ray diffraction measurements, continuous-wave X-band electron paramagnetic resonance (EPR) spectra, 57Fe Mössßauer spectra, and DC magnetic susceptibility data revealed that complex 1 exhibited a gradual and complete spin crossover at a transition temperature of 212 K, while complex 2 undergoes an incomplete spin crossover even at 400 K. Full article
(This article belongs to the Special Issue Stimuli-Responsive Magnetic Molecular Materials)
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Review

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14 pages, 2396 KiB  
Review
Spin Crossover and Magnetic-Dielectric Bistability Induced by Hidden Pseudo-Jahn–Teller Effect
by Isaac B. Bersuker
Magnetochemistry 2020, 6(4), 64; https://0-doi-org.brum.beds.ac.uk/10.3390/magnetochemistry6040064 - 22 Nov 2020
Cited by 3 | Viewed by 2777
Abstract
In a semi-review paper, we show that the hidden Jahn–Teller effect (JTE) and pseudo-JTE (PJTE) in molecular systems and solids, under certain conditions lead to the formation of two coexisting stable space configurations with different magnetic and dielectric properties, switchable by external perturbations. [...] Read more.
In a semi-review paper, we show that the hidden Jahn–Teller effect (JTE) and pseudo-JTE (PJTE) in molecular systems and solids, under certain conditions lead to the formation of two coexisting stable space configurations with different magnetic and dielectric properties, switchable by external perturbations. One of the stable configurations has a high space symmetry and a non-zero or higher spin (HS) (non-zero magnetic moment), the other being distorted, but with zero or lower spin (LS). The number of systems with hidden JTE or PJTE is innumerable; we demonstrate this on the (no exhaustible, too) group of systems with half-filed closed-shell degenerate electronic (orbital or band) configurations e2 and t3. The spin-crossover-change from the high symmetry HS arrangement to the low-symmetry LS geometry is accompanied by (driven by the PJTE) orbital disproportionation, in which the system prefers spins-paired states with two electrons on the same orbital (and lower symmetry charge distribution) over the Hund’s spin-parallel arrangement involving several orbitals. Ab initio calculations previously carried out on a series of molecular systems and clusters in crystals, including CuF3, Si3, Si4, Ge4, C4H4, Na4−, C603−, CuO6 (in two crystal environments, LiCuO2 and NaCuO2), etc., confirmed the general theory and allowed for estimates of the parameter values including relaxation times. The hidden JTE and PJTE are thus general tools for search and studies of polyatomic systems with bistabilities. Full article
(This article belongs to the Special Issue Stimuli-Responsive Magnetic Molecular Materials)
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