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Magnetochemistry
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Free Radicals: An Old Fashion Tool for Futures Multifunctional Magnetic...
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Free Radicals: An Old Fashion Tool for Futures Multifunctional Magnetic Materials

A special issue of Magnetochemistry (ISSN 2312-7481).

Deadline for manuscript submissions: closed (31 March 2018) | Viewed by 12141

Special Issue Editors

Dr. Catherine Hirel

E-Mail Website
Guest Editor
Chemistry Department, Gebze Technical University, 41400 Gebze Kocaeli, Turkey
Interests: syntheses of porphyrin, phthalocyanine and nitronyl/imino nitroxide derivatives; radical ligand; polyradical; luminescence
Prof. Dr. Dominique Luneau

E-Mail Website
Guest Editor
Laboratoire des Multimatériaux et Interfaces (UMR 5615), Université Claude Bernard Lyon 1, 69622 Villeurbanne cedex, France
Interests: molecular magnetism and crystallography; coordination chemistry for the engineering of molecular materials with dedicated physical properties

Special Issue Information

Dear Colleagues,

Alongside the inorganic transition and lanthanide metal ions, organic free radicals have had a leading role in the early development of molecule-based magnets. This certainly holds in the beginning, partly because free radicals are by nature molecular spin-carriers and departs from classic magnets, in contrast to inorganic metal ions. Moreover, as specific of organic chemistry there is the rich palette of potential variations attached to free radicals. Free radicals have been investigated (with some notable success) in magnetism as molecular bricks of purely organic magnets. Further enthusiasm for free radicals has came when nitronyl nitroxide radicals were used as bridging ligands in so-called metal-radicals, presenting the marriage of organic and inorganic spin-carriers.

The molecular magnetism community has been moving towards single-molecule magnets; however, due to their lack of magnetic anisotropy, there have been less efforts, but the field is still active. Moreover, the growing interest in redox-active ligands, as well as radical-based polymeric materials, promising charge transporting and storable materials, makes free radicals promising for magnetic multifunctional materials.

In this context, we believe this Special Issue of Magnetochemistry provides an opportunity to discuss the state-of-the-art of free radicals, without any restrictions, but work that also includes original work in synthesis and investigation, dedicated to magnetism and prospects in functional materials.

Dr. Catherine Hirel
Prof. Dominique Luneau
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

  • Organic magnet

  • Single-molecule magnets

  • Coordination polymer

  • Bistability

  • Magneto-optical and conductive properties

Published Papers (3 papers)

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10 pages, 1575 KiB  
Article
One-Dimensional Chain-Type Dicopper Coordination Polymer Linked by 1,4-Di(4-pyridyl)benzene; Synthesis, Crystal Structure, Magnetic Property, and Gas-Adsorption Property
by Natsumi Yano, Makoto Handa, Minoru Mitsumi and Yusuke Kataoka
Magnetochemistry 2018, 4(2), 26; https://doi.org/10.3390/magnetochemistry4020026 - 11 Jun 2018
Cited by 1 | Viewed by 3347
Abstract
A one-dimensional chain-type dicopper(II) coordination polymer with 1,4-di(4-pyridyl)-benzene (dpybz), [Cu2(O2C-tBu)4(dpybz)] (1), is synthesized and characterized by single crystal X-ray diffraction, infrared spectroscopy, and CHN elemental analysis. Single crystal X-ray diffraction confirms that the [...] Read more.
A one-dimensional chain-type dicopper(II) coordination polymer with 1,4-di(4-pyridyl)-benzene (dpybz), [Cu2(O2C-tBu)4(dpybz)] (1), is synthesized and characterized by single crystal X-ray diffraction, infrared spectroscopy, and CHN elemental analysis. Single crystal X-ray diffraction confirms that the one-dimensional chains of 1 are assembled with CH···π interactions at the dpybz moieties to form a brick-like porous network structure. Magnetic susceptibility measurement and broken-symmetry density functional theory (BS-DFT) calculations indicate that (i) antiferromagnetic interactions are present between two copper ions through the bridging carboxylate ligands; the observed exchange integral value (J) of 1 is −175.3 cm−1, which is consistent with the DFT-calculated value for 1 (−174.5 cm−1), and (ii) the magnetic interaction between two Cu2 units through the dpybz ligand is negligible. N2 adsorption measurements indicate that the porous structure of 1 is retained even after evacuation of the guest solvents from the pores of 1, and 1 adsorbs N2 molecules into its pores (the Langmuir surface area of 1 is estimated as 538.0 m2/g). Full article
(This article belongs to the Special Issue Free Radicals: An Old Fashion Tool for Futures Multifunctional Magnetic Materials)
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16 pages, 3984 KiB  
Article
Chain Compounds Based on Paddle-wheel Copper(II) Carboxylate Bearing Four Nitroxide Radicals
by Masahiro Mikuriya, Renny Indrawati, Rieko Hashido, Shizuka Matsubara, Chizu Nakamura, Daisuke Yoshioka, Kazuyuki Yokota, Masafumi Fukuzaki and Makoto Handa
Magnetochemistry 2018, 4(2), 22; https://doi.org/10.3390/magnetochemistry4020022 - 10 May 2018
Cited by 12 | Viewed by 4543
Abstract
Chain compounds of paddle-wheel Cu2-clusters of 3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidinyloxy (Hcaproxy) and 4-carboxy-2,2,6,6-tetramethylpiperidinyloxy (Hcatempo) and N,N’-bidentate ligands (L = 4,4′-bipyridine (4,4′-bpy), 1,2-bis(4-pyridyl)ethane (bpe), trans-1,2-bis(4-pyridyl)ethylene (bpel), 4,4′-dipyridyl disulfide (pds), 1,4-diazabicyclo[2.2.2]octane (dabco), and pyrazine (pyz)), [Cu2(caproxy)4(L)]n, [...] Read more.
Chain compounds of paddle-wheel Cu2-clusters of 3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidinyloxy (Hcaproxy) and 4-carboxy-2,2,6,6-tetramethylpiperidinyloxy (Hcatempo) and N,N’-bidentate ligands (L = 4,4′-bipyridine (4,4′-bpy), 1,2-bis(4-pyridyl)ethane (bpe), trans-1,2-bis(4-pyridyl)ethylene (bpel), 4,4′-dipyridyl disulfide (pds), 1,4-diazabicyclo[2.2.2]octane (dabco), and pyrazine (pyz)), [Cu2(caproxy)4(L)]n, and [Cu2(catempo)4(L)]n, were synthesized and characterized by elemental analysis, infrared and UV-vis spectra and temperature dependence of magnetic susceptibilities (4.5–300 K). The crystal structures of [Cu2(caproxy)4(pds)]n, [Cu2(catempo)4(4,4′-bpy)]n, and [Cu2(catempo)4(bpe)]n revealed zigzag or linear chains consisting of alternate arrangement of the dinuclear cluster bearing four nitroxide radicals and N,N’-bidentate ligand. Temperature dependence of magnetic susceptibilities showed a considerable antiferromagnetic interaction between the two copper(II) ions within the dinuclear cluster, and weak antiferromagnetic interaction between the dinuclear clusters and/or the radical and dinuclear cluster. Full article
(This article belongs to the Special Issue Free Radicals: An Old Fashion Tool for Futures Multifunctional Magnetic Materials)
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12 pages, 3403 KiB  
Article
Synthesis, Structure and Magnetic and Electrochmical Properties of Tetrakis(benzamidato)diruthenium(II,III) Tetrafluoroborate
by Makoto Handa, Natsumi Yano, Airi Okuno, Hiroki Nakai, Minoru Mitsumi, Masahiro Mikuriya and Yusuke Kataoka
Magnetochemistry 2018, 4(2), 21; https://doi.org/10.3390/magnetochemistry4020021 - 01 May 2018
Cited by 2 | Viewed by 3693
Abstract
A lantern-type diruthenium(II,III) complex [Ru2(HNOCPh)4(BF4)(H2O)] was prepared from [Ru2(HNOCPh)4Cl]n by removal of the axial chlorido-bridge using AgBF4 in THF. The room temperature magnetic moment (per Ru25+ unit) [...] Read more.
A lantern-type diruthenium(II,III) complex [Ru2(HNOCPh)4(BF4)(H2O)] was prepared from [Ru2(HNOCPh)4Cl]n by removal of the axial chlorido-bridge using AgBF4 in THF. The room temperature magnetic moment (per Ru25+ unit) of [Ru2(HNOCPh)4(BF4)(H2O)] is 3.84 μB, which is similar to that (4.15 μB) of [Ru2(HNOCPh)4Cl]n, for which magnetic measurement was newly performed in this study. These results indicate that both of the complexes have a spin state of S = 3/2, although temperature-variable (VT) magnetic moments (2–300 K) showed that considerable antiferromagnetic interaction (zJ = −2.8 cm−1) exists through the axial chlorido-bridge for [Ru2(HNOCPh)4Cl]n, but such a large interaction (zJ = −0.08 cm−1) does not exist for [Ru2(HNOCPh)4(BF4)(H2O)], where the large zero-field splitting D = 61 cm−1 is operative for both complexes, like other lantern-type diruthenium(II,III) complexes. The X-ray single-crystal structure analysis of [Ru2(HNOCPh)4(BF4)(H2O)]·2(acetone) showed that the axial positions of the complex were occupied by a fluorine atom of the BF4− ion and an oxygen atom of the water molecule, with distances of Ru-Fax = 2.3265(19) Å and Ru-Oax = 2.280(2) Å, respectively. The Ru-Ru bond distance was 2.2793(4) Å, which is shorter than those (2.295(2) and 2.290(2) Å) reported for [Ru2(HNOCPh)4Cl]n. The quartet ground states (S = 3/2) were reasonably interpreted for [Ru2(HNOCPh)4(BF4)(H2O)] and [Ru2(HNOCPh)4Cl]n, as well as the theoretically modeled complex cation [Ru2(HNOCPh)4]+, by DFT calculation results. A Ru26+/Ru25+ redox couple was observed at 1.12 V (vs. SCE) for [Ru2(HNOCPh)4(BF4)(H2O)] in dichloromethane containing Bu4NPF6 as electrolyte. Full article
(This article belongs to the Special Issue Free Radicals: An Old Fashion Tool for Futures Multifunctional Magnetic Materials)
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