Advances in Molecular Magnetism

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

Deadline for manuscript submissions: closed (15 August 2023) | Viewed by 10797

Special Issue Editors


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Guest Editor
School of Materials Science and Engineering, Nankai University, Tianjin 300350, China
Interests: molecular magnets; magnetic properties; supramolecular assembly; metal–organic frameworks
Special Issues, Collections and Topics in MDPI journals

E-Mail Website
Guest Editor
School of Materials Science and Engineering, Nankai University, Tianjin 300350, China
Interests: single-molecule magnets

Special Issue Information

Dear Colleagues,

This Special Issue entitled “Advances in Molecular Magnetism” aims to provide a valuable forum wherein scientists in the research field of molecular magnetism will be able to share their most recent novel findings on the synthesis of new compounds and switching the magnetic properties of advanced molecular materials.

Topics to be covered include but are not limited to:

  • Molecular magnets: spin-crossover (SCO); valence tautomerism (VT); charge transfer (CT); single-chain magnets (SCMs); single-molecule magnets (SMMs); spin frustration; magnetic refrigerators; light-, pressure-, and electric-responsive magnetic molecular materials; magnetic metal–organic frameworks; slow magnetic relaxation; and organic radicals.

We hope to establish a collection of papers that will be of interest to scholars in the field. Contributions in the form of full papers, reviews, and communications about the related topics are very welcome.

Dr. Zhao-Yang Li
Dr. Quan-Wen Li
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.

Keywords

  • molecular-based magnets
  • spin-crossover
  • single-molecule magnets
  • single-chain magnets
  • organic radicals

Published Papers (6 papers)

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Research

15 pages, 2237 KiB  
Article
A Chain of Vertex-Sharing {CoIII2CoII2}n Squares with Single-Ion Magnet Behavior
by Maria-Gabriela Alexandru, Diana Visinescu, Sergiu Shova, Joan Cano, Nicolás Moliner, Francesc Lloret and Miguel Julve
Magnetochemistry 2023, 9(5), 130; https://doi.org/10.3390/magnetochemistry9050130 - 15 May 2023
Viewed by 1483
Abstract
A new mixed-valence one-dimensional coordination polymer of formula {[CoII(MeOH)2][(μ-NC)2CoIII(dmphen)(CN)2]2}n·2nH2O (1) was obtained by reacting the Ph4P[CoII(dmphen)(CN)3 [...] Read more.
A new mixed-valence one-dimensional coordination polymer of formula {[CoII(MeOH)2][(μ-NC)2CoIII(dmphen)(CN)2]2}n·2nH2O (1) was obtained by reacting the Ph4P[CoII(dmphen)(CN)3] metalloligand (dmphen = 2,9-dimethyl-1,10-phenanthroline and Ph4P+ = tetraphenylphosphonium ion) with cobalt(II) acetate tetrahydrate. The structural analysis shows the formation of a neutral 4,2-ribbon-like chain of vertex-sharing cyanido-bridged {CoIII2CoII2} squares in which the metalloligand underwent an oxidation process and a reorganization to form {CoIII(dmphen)(CN)4} linkers that coordinate to the [CoII(MeOH)2]2+ units through single cyanido ligands. Both cobalt(II) and Co(III) cations are six-coordinated in distorted octahedral environments. The shortest intrachain distance between the paramagnetic cobalt(II) ions is 7.36 Å, a value which is shorter than the shortest interchain one (10.36 Å). Variable-temperature (1.9–300 K) static (dc) magnetic measurements for 1 indicate the occurrence of magnetically isolated high-spin cobalt(II) ions with a D value of +67.0 cm−1. Dynamic alternating current (ac) magnetic measurements between 2.0–13 K reveal that 1 exhibits slow magnetic relaxation under non-zero applied dc fields, being thus a new example of field-induced SIM with easy-plane magnetic anisotropy. Theoretical calculations by CASSCF/NEVPT2 on 1 support the results from magnetometry. The relaxation of the magnetization occurs in the ground state under external dc fields through a two-phonon Raman process and one intra-Kramers mechanism. Full article
(This article belongs to the Special Issue Advances in Molecular Magnetism)
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10 pages, 2081 KiB  
Article
A Cu12 Metallacycle Assembled from Four C3-Symmetric Spin Frustrated Triangular Units
by Basharat Ali, Grégoire David, Frédéric Gendron, Xiao-Lei Li, Olivier Cador, Winfried Plass, Boris Le Guennic and Jinkui Tang
Magnetochemistry 2023, 9(5), 122; https://doi.org/10.3390/magnetochemistry9050122 - 6 May 2023
Viewed by 1482
Abstract
Assembling metallacycles with interesting topological arrangements is a critical task for chemists. We report here a novel dodecanuclear CuII compound, [{Cu3L(µ-N3)}4(Py)14]·2Py (Cu12) (where Py = pyridine and [H6L]Cl = [...] Read more.
Assembling metallacycles with interesting topological arrangements is a critical task for chemists. We report here a novel dodecanuclear CuII compound, [{Cu3L(µ-N3)}4(Py)14]·2Py (Cu12) (where Py = pyridine and [H6L]Cl = tris(2-hydroxybenzylidine)triaminoguanidinium chloride, respectively), with the topology of a cycle accomplished by four two-connecting approximately flat C3-symmetric guanidine-based ligands. Each ligand affords three tridentate metal-binding cavities and the four node-to-node connections through single azido bridges are provided by pairs of metal centers. A theoretical investigation using CASSCF in addition to DFT calculations showed strong antiferromagnetic coupling within the Cu3-triangles, resulting in spin-frustrated systems. However, these calculations were not able to properly reproduce the very weak antiferromagnetic couplings between the triangle units, highlighting the challenge of describing the magnetic behavior of this compound. Full article
(This article belongs to the Special Issue Advances in Molecular Magnetism)
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11 pages, 2283 KiB  
Article
Diverse Magnetic Properties of Two New Binuclear Complexes Affected by [FeN6] Octahedral Distortion: Two-Step Spin Crossover versus Antiferromagnetic Interactions
by Yue Gao, Yu-Qin Li, Yao Li, Jing-Wei Dai, Jin-Hua Wang, Ying-Ying Wu, Masahiro Yamashita and Zhao-Yang Li
Magnetochemistry 2023, 9(3), 69; https://doi.org/10.3390/magnetochemistry9030069 - 28 Feb 2023
Viewed by 1364
Abstract
Polymetallic complexes with covalently bridged metal centers that interact magnetically are important in the molecular magnetism field, with binuclear compounds receiving special attention because they represent the simplest type of multinuclear species with covalently bridged metal centers. Herein, we report the synthesis and [...] Read more.
Polymetallic complexes with covalently bridged metal centers that interact magnetically are important in the molecular magnetism field, with binuclear compounds receiving special attention because they represent the simplest type of multinuclear species with covalently bridged metal centers. Herein, we report the synthesis and properties of two new binuclear FeII complexes, namely, {[Fe(abpt-TPE)(NCS)2]2(bpym)}·2MeOH·2MeCN (1) and {[Fe(abpt-TPE)(NCS)2]2(bpym)}·2CH2Cl2 (2) (bpym = 2,2′-bipyrimidine). The crystal structure is analyzed at different temperatures, and its properties are analyzed by variable-temperature magnetic susceptibility and variable-temperature fluorescence emission spectroscopy tests. Variable-temperature magnetic susceptibility measurements of two binuclear compounds show different types of magnetic behavior. Complex 1 exhibits two-step spin transition behavior with an intermediate state near 150 K (Tc1 = 191 K, Tc2 = 111 K); 1 undergoes an [LS–LS] ↔ [LS–HS] ↔ [HS–HS] spin transition during thermal induction. On the other hand, complex 2 exhibits intramolecular antiferromagnetic coupling, with J = −0.47 cm−1. The analysis of correlations between the structural characteristics and different types of magnetic behaviors for two binuclear complexes, revealed that the different magnetic behaviors shown by the two complexes are attributable to different degrees of [FeN6] octahedral distortion caused by different lattice solvents, ligand strain and crystal stacking. Full article
(This article belongs to the Special Issue Advances in Molecular Magnetism)
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14 pages, 2744 KiB  
Article
Surface-Bulk 2D Spin-Crossover Nanoparticles within Ising-like Model Solved by Using Entropic Sampling Technique
by Catherine Cazelles, Mamadou Ndiaye, Pierre Dahoo, Jorge Linares and Kamel Boukheddaden
Magnetochemistry 2023, 9(3), 61; https://doi.org/10.3390/magnetochemistry9030061 - 23 Feb 2023
Cited by 1 | Viewed by 1326
Abstract
We model the thermal effects in different 2D spin-crossover (SCO) square lattices within the frame of the Ising-like model using Monte Carlo entropic sampling (MCES) method to enhance the scan of macrostates beyond the most probable thermal ones. In fact, MCES allows access [...] Read more.
We model the thermal effects in different 2D spin-crossover (SCO) square lattices within the frame of the Ising-like model using Monte Carlo entropic sampling (MCES) method to enhance the scan of macrostates beyond the most probable thermal ones. In fact, MCES allows access to the metastable states, and it is then well adapted to study thermal hysteresis properties. In this contribution, we distinguish, for the first time, the interaction between molecules located in bulk at the surface and those connecting the bulk and surface regions of an SCO lattice. In addition, an extra ligand field contribution is assigned to surface molecules through an interaction parameter L. In the absence of environmental effects on surface nanoparticles, a single thermal hysteresis loop increasing with the lattice size is simulated with a unique bulk and surface equilibrium temperature Teq=Teqbulk= Teqsurf. When environmental effects are accounted for, a two-step behavior associated with two hysteresis loops of widths ΔTS (for the surface) and ΔTB (for the bulk) with an intermediate plateau 14 K wide is obtained in the thermal dependence of the high-spin (HS) fraction for the 6 × 6 lattice. The surface and bulk equilibrium temperatures are then different, both decreasing towards lower values, and the L parameter controls the three states’ behavior as well as the hysteresis loop interval. Size effects show that the equilibrium temperature is governed by the surface atoms for a small lattice size (5 × 5) and by the bulk atoms for a large lattice size (7 × 7). Moreover, a change in the size of the lattice results in a variation of the order–disorder (or Curie) temperature, TO.D., and the surface equilibrium temperature, Teq, while only TO.D. changes in bulk. Full article
(This article belongs to the Special Issue Advances in Molecular Magnetism)
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10 pages, 2825 KiB  
Article
Zero-Field Splitting in Cyclic Molecular Magnet {Cr8Y8}: A High-Frequency ESR Study
by Zhendong Fu, Zhong-Wen Ouyang, Qian-Cheng Luo, Yan-Zhen Zheng, Wei Tong, Huanpeng Bu, Hanjie Guo and Jin-Kui Zhao
Magnetochemistry 2023, 9(2), 49; https://doi.org/10.3390/magnetochemistry9020049 - 3 Feb 2023
Viewed by 1446
Abstract
Cyclic 3d-4f molecular magnets have received considerable attention owing to their potential applications in high-density data storage and quantum information processing. As a rare example of ferromagnetic polynuclear Cr rings, {Cr8Y8} represents a valuable test bed to directly study [...] Read more.
Cyclic 3d-4f molecular magnets have received considerable attention owing to their potential applications in high-density data storage and quantum information processing. As a rare example of ferromagnetic polynuclear Cr rings, {Cr8Y8} represents a valuable test bed to directly study the magnetic interaction between Cr3+ ions in large hexadecametallic {Cr8Ln8} (Ln = 4f metal) molecules. We have proposed a “single-J” model to approximate the low-temperature spin dynamics of {Cr8Y8} in our earlier study, while a zero-field splitting (ZFS) of the quantum levels was also suggested by the heat capacity data. In order to have a deeper understanding of the magnetism of {Cr8Y8}, it is necessary to verify the ZFS by means of high-resolution spectral methods and identify its origin. In this work, we present a high-frequency electron spin resonance (HF-ESR) study on the ZFS of {Cr8Y8}. The X-band ESR spectra consists of multi-peak structure, indicative of magnetic anisotropy that breaks the degeneracy between spin states in the absence of a magnetic field. HF-ESR spectra are collected to extract the ZFS parameters. We observed a sharp resonance peak due to the transitions between the S = 11 quantum levels and a broadband corresponding to a distribution of resonance peaks due to the ZFS of the S = 12 quantum levels. By analyzing HF-ESR spectra, we confirm the expected S = 12 ground state and determine its ZFS parameter D as −0.069 K, and, furthermore, we reproduce the spectra recorded at 154 GHz. The macrospin model proves to still be valid. The ZFS is attributed to the axial magnetic anisotropy, as found in some other Cr-based molecular wheels. The detailed HF-ESR investigation presented in this paper will benefit the studies on other {Cr8Ln8} wheels with magnetic Ln3+ ions and highlights the importance of the HF-ESR method as a high-resolution probe in determining the ZFS parameters with very small magnitude. Full article
(This article belongs to the Special Issue Advances in Molecular Magnetism)
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9 pages, 3489 KiB  
Article
Chiral Dy(III) Fluorescent Single-Molecule Magnet Based on an Achiral Flexible Ligand
by Min Zeng, Lin Miao, Xue-Ru Wu, Cai-Ming Liu and Hui-Zhong Kou
Magnetochemistry 2022, 8(12), 166; https://doi.org/10.3390/magnetochemistry8120166 - 23 Nov 2022
Cited by 5 | Viewed by 1872
Abstract
A novel multi-channel barcode module was developed by using chiral co-crystals which contain field-induced SMM behavior and different emission bands. The chiral co-crystals [Zn(H2L)Dy(DBM)2]4(ClO4)4⋅9CH3OH⋅H2O (1a) and [Zn(H [...] Read more.
A novel multi-channel barcode module was developed by using chiral co-crystals which contain field-induced SMM behavior and different emission bands. The chiral co-crystals [Zn(H2L)Dy(DBM)2]4(ClO4)4⋅9CH3OH⋅H2O (1a) and [Zn(H2L)Dy(DBM)2]4(ClO4)4⋅8CH3OH⋅0.5H2O (1b) (H4L = 2,2′-[1,2-ethanediylbis[(hydroxyethylimino)methylene]]bis[6-methoxy-4-methyl-phenol], HDBM = dibenzoylmethane) were obtained through one-pot reaction of ZnII and DyIII with the achiral ligands H4L and HDBM. X-ray single crystal diffraction and CD spectroscopy confirmed that they are enantiomers crystallized in P43 (1a) and P41 (1b), both consisting of two ∆-[Zn(H2L)Dy(DBM)2]+ cations, two Λ-[Zn(H2L)Dy(DBM)2]+ cations and four (ClO4) anions. The presence of DyIII ions endow them with the property of field-induced slow magnetic relaxation. The relatively low energy barrier of 35.0(9) K for complex 1 may be due to the poor axiality of the ligand field caused by the long Dy-Ophenoxy bond lengths and the small Ophenoxy-Dy-Ophenoxy bond angles. Moreover, when the organic ligands H4L (λex = 350 nm) and DyIIIex = 420 nm) are excited, different emission spectra are observed. Full article
(This article belongs to the Special Issue Advances in Molecular Magnetism)
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