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Magnetochemistry, Volume 2, Issue 4 (December 2016)

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Research

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Open AccessArticle Magneto-Luminescence Correlation in the Textbook Dysprosium(III) Nitrate Single-Ion Magnet
Magnetochemistry 2016, 2(4), 41; doi:10.3390/magnetochemistry2040041
Received: 11 October 2016 / Revised: 10 November 2016 / Accepted: 12 November 2016 / Published: 18 November 2016
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Abstract
Multifunctional Single-Molecule Magnets (SMMs) or Single-Ion Magnets (SIMs) are intriguing molecule-based materials presenting an association of the slow magnetic relaxation with other physical properties. In this article, we present an example of a very simple molecule based on Dy3+ ion exhibiting a
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Multifunctional Single-Molecule Magnets (SMMs) or Single-Ion Magnets (SIMs) are intriguing molecule-based materials presenting an association of the slow magnetic relaxation with other physical properties. In this article, we present an example of a very simple molecule based on Dy3+ ion exhibiting a field induced SIM property and a characteristic Dy3+ based emission. The [Dy(NO3)3(H2O)4]·2H2O (1) complex is characterized by the means of single crystal X-Ray diffraction and their magnetic and photo-luminescent properties are investigated. We demonstrate here that it is possible to correlate the magnetic and luminescent properties and to obtain the Orbach barrier from the low temperature emission spectra, which is often difficult to properly extract from the magnetic measurements, especially in the case of field induced SIMs. Full article
(This article belongs to the Special Issue Molecular Magnetism of Lanthanides Complexes and Networks)
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Open AccessArticle Slow Magnetic Relaxation of Lanthanide(III) Complexes with a Helical Ligand
Magnetochemistry 2016, 2(4), 43; doi:10.3390/magnetochemistry2040043
Received: 31 October 2016 / Revised: 28 November 2016 / Accepted: 30 November 2016 / Published: 8 December 2016
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Abstract
Isostructural Ln(III) mononuclear complexes [Ln(NO3)2L]PF6·MeCN (Ln = Nd, Tb, or Dy; L denotes a helical hexa-dentate ligand) were synthesized, and their slow magnetic relaxation behavior was investigated. In these complexes, oblate-type Ln(III) ions are located in an
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Isostructural Ln(III) mononuclear complexes [Ln(NO3)2L]PF6·MeCN (Ln = Nd, Tb, or Dy; L denotes a helical hexa-dentate ligand) were synthesized, and their slow magnetic relaxation behavior was investigated. In these complexes, oblate-type Ln(III) ions are located in an axially stressed ligand field with two nitrate anions, and can exhibit single-molecule magnet (SMM) behavior. Field-induced SMM behavior was observed for Nd(III) and Dy(III) complexes under an applied bias DC field of 1000 Oe. Full article
(This article belongs to the Special Issue Molecular Magnetism of Lanthanides Complexes and Networks)
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Open AccessArticle Hybrid Molecular Compound Exhibiting Slow Magnetic Relaxation and Electrical Conductivity
Magnetochemistry 2016, 2(4), 44; doi:10.3390/magnetochemistry2040044
Received: 27 September 2016 / Revised: 28 November 2016 / Accepted: 30 November 2016 / Published: 9 December 2016
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Abstract
Electrochemical oxidation of a solution containing KDy(hfac)4 (hfac, hexafluoroacetyacetone) and Bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) afforded a hybrid material formulated as [β′-(BEDT-TTF)2Dy(CF3COO)4∙MeCN]n. The complex crystallizes in the triclinic space group P1¯. The before mentioned
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Electrochemical oxidation of a solution containing KDy(hfac)4 (hfac, hexafluoroacetyacetone) and Bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) afforded a hybrid material formulated as [β′-(BEDT-TTF)2Dy(CF3COO)4∙MeCN]n. The complex crystallizes in the triclinic space group P 1 ¯ . The before mentioned complex has a chain structure containing 4f ions bridged by mono-anion CF3COO ligand, and acts as single-molecule magnet (SMM) at low temperature. The conducting layer was composed of partially oxidized BEDT-TTF molecules in β′ type arrangement. The presence of radical cation and its charge ordering was assigned on the basis of optical spectra. Electrical resistivity measurements revealed semiconducting behaviour (conductivity at room temperature of 1.1 × 10−3 S·cm−1, activation energy of 158.5 meV) at ambient pressure. Full article
(This article belongs to the Special Issue Molecular Magnetism of Lanthanides Complexes and Networks)
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Open AccessFeature PaperArticle Synthesis and Characterization of Ethylenedithio-MPTTF-PTM Radical Dyad as a Potential Neutral Radical Conductor
Magnetochemistry 2016, 2(4), 46; doi:10.3390/magnetochemistry2040046
Received: 3 November 2016 / Revised: 7 December 2016 / Accepted: 9 December 2016 / Published: 16 December 2016
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Abstract
During the last years there has been a high interest in the development of new purely-organic single-component conductors. Very recently, we have reported a new neutral radical conductor based on the perchlorotriphenylmethyl (PTM) radical moiety linked to a monopyrrolo-tetrathiafulvalene (MPTTF) unit by a
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During the last years there has been a high interest in the development of new purely-organic single-component conductors. Very recently, we have reported a new neutral radical conductor based on the perchlorotriphenylmethyl (PTM) radical moiety linked to a monopyrrolo-tetrathiafulvalene (MPTTF) unit by a π-conjugated bridge (1) that behaves as a semiconductor under high pressure. With the aim of developing a new material with improved conducting properties, we have designed and synthesized the radical dyad 2 which was functionalized with an ethylenedithio (EDT) group in order to improve the intermolecular interactions of the tetrathiafulvalene (TTF) subunits. The physical properties of the new radical dyad 2 were studied in detail in solution to further analyze its electronic structure. Full article
(This article belongs to the Special Issue Magnetism of Molecular Conductors)
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Open AccessFeature PaperArticle Supramolecular Complexes for Quantum Simulation
Magnetochemistry 2016, 2(4), 37; doi:10.3390/magnetochemistry2040037
Received: 29 July 2016 / Revised: 20 September 2016 / Accepted: 26 September 2016 / Published: 1 October 2016
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Abstract
Simulating the evolution of quantum systems on a classical computer is a yellow very challenging task, which could be easily tackled by digital quantum simulators. These are intrinsically quantum devices whose parameters can be controlled in order to mimic the evolution of a
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Simulating the evolution of quantum systems on a classical computer is a yellow very challenging task, which could be easily tackled by digital quantum simulators. These are intrinsically quantum devices whose parameters can be controlled in order to mimic the evolution of a broad class of target Hamiltonians. We describe here a quantum simulator implemented on a linear register of molecular Cr7Ni qubits, linked through Co2+ ions which act as switches of the qubit–qubit interaction. This allows us to implement one- and two-qubit gates on the chain with high-fidelity, by means of uniform magnetic pulses. We demonstrate the effectiveness of the scheme by numerical experiments in which we combine several of these elementary gates to implement the simulation of the transverse field Ising model on a set of three qubits. The very good agreement with the expected evolution suggests that the proposed architecture can be scaled to several qubits. Full article
(This article belongs to the Special Issue Molecules in Quantum Information)
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Open AccessArticle Magnetic Behavior of Carboxylate and β-Diketonate Lanthanide Complexes Containing Stable Organometallic Moieties in the Core-Forming Ligand
Magnetochemistry 2016, 2(4), 38; doi:10.3390/magnetochemistry2040038
Received: 28 July 2016 / Revised: 26 September 2016 / Accepted: 28 September 2016 / Published: 10 October 2016
Cited by 2 | PDF Full-text (4108 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Information concerning the structures of compounds of rare earth elements with carboxylic acids and a β-diketone containing stable organometallic moieties that we obtained previously is presented. Additional results for 15 complexes with the [Gd2O2] core allowed confirming and improving
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Information concerning the structures of compounds of rare earth elements with carboxylic acids and a β-diketone containing stable organometallic moieties that we obtained previously is presented. Additional results for 15 complexes with the [Gd2O2] core allowed confirming and improving the correlation between JGd–Gd′ and the Gd…Gd distance for complexes of this type that we found earlier. For the first time, dc and ac magnetic measurements were carried out for the formerly-described complex [Dy2(O2CCym)4(NO3)2(DMSO)4] (2), Cym = (η5-C5H4)Mn(CO)3), and two new binuclear complexes, namely [Dy2(O2CFc)4(NO3)2(DMSO)4] (3), and [Dy2(O2CFc)6(DMSO)2(H2O)2] (4), Fc = (η5-C5H4)Fe(η5-C5H5)). For binuclear [Dy2(O2CCym)6(DMSO)4] (1), as well as for a 1D-polymer [Dy(O2CCym)(acac)2(H2O)]n (6), ac magnetic measurements were carried out more precisely. The characteristics of a single-molecule magnet and of a single-chain magnet were determined for Complexes 2 and 6, respectively. Full article
(This article belongs to the Special Issue Molecules in Quantum Information)
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Open AccessArticle Strain Engineering of the CeNi5 System
Magnetochemistry 2016, 2(4), 39; doi:10.3390/magnetochemistry2040039
Received: 16 August 2016 / Revised: 27 September 2016 / Accepted: 19 October 2016 / Published: 1 November 2016
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Abstract
The effect of strain on the CeNi5 system has been investigated using density functional theory (DFT). The studies have shown that localised Ce 4f and Ni 3d states carry the magnetic moment of the material. The Ce 4f moment remains relatively unchanged
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The effect of strain on the CeNi5 system has been investigated using density functional theory (DFT). The studies have shown that localised Ce 4f and Ni 3d states carry the magnetic moment of the material. The Ce 4f moment remains relatively unchanged during strain whereas the Ni 3d moment increases as the strain becomes increasingly tensile in both the basal and non-basal directions. A significant strain-dependent interaction exists between delocalised, non-magnetic Ce 6s–Ni 4s states. A weaker group of Ni 3d–Ce 6s/Ni 4s and Ni 3d–Ni 3d interactions exist, indicating that competing localised and delocalised mechanisms act on the Ni 3d states during strain. Full article
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Review

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Open AccessFeature PaperReview The Rise of Single-Ion Magnets as Spin Qubits
Magnetochemistry 2016, 2(4), 40; doi:10.3390/magnetochemistry2040040
Received: 31 August 2016 / Revised: 8 October 2016 / Accepted: 25 October 2016 / Published: 16 November 2016
Cited by 2 | PDF Full-text (11359 KB) | HTML Full-text | XML Full-text
Abstract
Recent studies revealed that magnetic molecules with single spin centers showed exciting phenomena related to quantum information processing, such as long quantum coherence times and Rabi oscillations. In this review, we go over these phenomena according to the essential metal ions, from which
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Recent studies revealed that magnetic molecules with single spin centers showed exciting phenomena related to quantum information processing, such as long quantum coherence times and Rabi oscillations. In this review, we go over these phenomena according to the essential metal ions, from which we can see the development of single-ion magnets as spin qubits is booming, especially quantum coherence times have been significantly enhanced from nanoseconds to hundreds of microseconds in a short period. Hence, the correlations between the molecular structures and quantum coherence are becoming clearer. In this regard, some chemical approaches to designing better spin qubits have been discussed. Full article
(This article belongs to the Special Issue Molecules in Quantum Information)
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Open AccessFeature PaperReview Recent Advances in Organic Radicals and Their Magnetism
Magnetochemistry 2016, 2(4), 42; doi:10.3390/magnetochemistry2040042
Received: 5 October 2016 / Revised: 18 November 2016 / Accepted: 22 November 2016 / Published: 30 November 2016
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Abstract
The review presents an overview of the organic radicals that have been designed and synthesized recently, and their magnetic properties are discussed. The π-conjugated organic radicals such as phenalenyl systems, functionalized nitronylnitroxides, benzotriazinyl, bisthiazolyl, aminyl-based radicals and polyradicals, and Tetrathiafulvalene (TTF)-based H-bonded radicals
[...] Read more.
The review presents an overview of the organic radicals that have been designed and synthesized recently, and their magnetic properties are discussed. The π-conjugated organic radicals such as phenalenyl systems, functionalized nitronylnitroxides, benzotriazinyl, bisthiazolyl, aminyl-based radicals and polyradicals, and Tetrathiafulvalene (TTF)-based H-bonded radicals have been considered. The examples show that weak supramolecular interactions play a major role in modulating the ferromagnetic and antiferromagnetic properties. The new emerging direction of zethrenes, organic polyradicals, and macrocyclic polyradicals with their attractive and discrete architectures has been deliberated. The magnetic studies delineate the singlet-triplet transitions and their corresponding energies in these organic radicals. We have also made an attempt to collate the major organic neutral radicals, radical ions and radical zwitterions that have emerged over the last century. Full article
(This article belongs to the Special Issue Molecules in Quantum Information)
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Open AccessReview Perspectives on Neutron Scattering in Lanthanide-Based Single-Molecule Magnets and a Case Study of the Tb2(μ-N2) System
Magnetochemistry 2016, 2(4), 45; doi:10.3390/magnetochemistry2040045
Received: 8 November 2016 / Revised: 24 November 2016 / Accepted: 25 November 2016 / Published: 14 December 2016
PDF Full-text (6161 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Single-molecule magnets (SMMs) based on lanthanide ions display the largest known blocking temperatures and are the best candidates for molecular magnetic devices. Understanding their physical properties is a paramount task for the further development of the field. In particular, for the poly-nuclear variety
[...] Read more.
Single-molecule magnets (SMMs) based on lanthanide ions display the largest known blocking temperatures and are the best candidates for molecular magnetic devices. Understanding their physical properties is a paramount task for the further development of the field. In particular, for the poly-nuclear variety of lanthanide SMMs, a proper understanding of the magnetic exchange interaction is crucial. We discuss the strengths and weaknesses of the neutron scattering technique in the study of these materials and particularly for the determination of exchange. We illustrate these points by presenting the results of a comprehensive inelastic neutron scattering study aimed at a radical-bridged diterbium(III) cluster, Tb2(μ-N23−), which exhibits the largest blocking temperature for a poly-nuclear SMM. Results on the YIII analogue Y2(μ-N23−) and the parent compound Tb2(μ-N22−) (showing no SMM features) are also reported. The results on the parent compound include the first direct determination of the lanthanide-lanthanide exchange interaction in a molecular cluster based on inelastic neutron scattering. In the SMM compound, the resulting physical picture remains incomplete due to the difficulties inherent to the problem. Full article
(This article belongs to the Special Issue Molecular Magnetism of Lanthanides Complexes and Networks)
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