Magnetic Slow Relaxation in a Metal–Organic Framework Made of Chains of Ferromagnetically Coupled Single‐Molecule Magnets

Huang, Gang; Garcia, Guglielmo Fernandez; Badiane, Insa; Camarra, Magatte; Freslon, Stéphane; Guillou, Olivier; Daiguebonne, Carole; Totti, Federico; Cador, Olivier; Guizouarn, Thierry; Guennic, Boris Le; Bernot, Kévin

doi:10.1002/chem.201800095

Cited by 74 publications

(48 citation statements)

References 145 publications

(145 reference statements)

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“…The atomic electric multipole moments were computed with the LOPROP module79 on the ground state electronic density obtained with the CASSCF/CASSI-SO method. The highly reliable80 LOPROP electrostatic charges, dipoles and quadrupoles computed for all the atoms in the DyDOTA models were employed as a basis for the analysis of the electrostatic field around the Ln ion, performed with the homemade CAMMEL (CAlculated Molecular Multipolar ELectrostatics) code 81–83…”

Section: Computational Detailsmentioning

confidence: 99%

Covalency and magnetic anisotropy in lanthanide single molecule magnets: the DyDOTA archetype

et al. 2019

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Section: Computational Detailsmentioning

confidence: 99%

Covalency and magnetic anisotropy in lanthanide single molecule magnets: the DyDOTA archetype

et al. 2019

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“…To describel ess symmetrical environments, computational approaches have recently been proposed that 1) combine an electrostatic description with semi-empirical radiale ffectivec harges (RECs) [11] and 2) describe the ligands by charges either optimized to fit the experimental data within the lone-pair effectivec harge( LPEC) model [12] or taken from ab initio calculations (CAMMEL). [13] Ap urely electrostatic approach has been proposed to determine the directiono ft he magnetic momentb ym inimizing the potential energy; the ligands are modeled by fractional charges determined by valence-bond resonance hybrids. [14] Even though the lanthanide-ion-ligand interaction is predominately electrostatic, some degree of covalency has been evidenced, but to al esser extent than for the 5f elements.…”

Section: Introductionmentioning

confidence: 99%

Derivation of Lanthanide Series Crystal Field Parameters From First Principles

Jung

Islam

Pecoraro

et al. 2019

Chemistry A European J

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Two series of lanthanide complexes have been chosen to analyze trends in the magnetic properties and crystal field parameters (CFPs) along the two series: The highly symmetric LnZn16(picHA)16 series (Ln=Tb, Dy, Ho, Er, Yb; picHA=picolinohydroxamic acid) and the [Ln(dpa)3](C3H5N2)3⋅3H2O series (Ln=Ce–Yb; dpa=2,6‐dipicolinic acid) with approximate three‐fold symmetry. The first series presents a compressed coordination sphere of eight oxygen atoms whereas in the second series, the coordination sphere consists of an elongated coordination sphere formed of six oxygen atoms. The CFPs have been deduced from ab initio calculations using two methods: The AILFT (ab initio ligand field theory) method, in which the parameters are determined at the orbital level, and the ITO (irreducible tensor operator) decomposition, in which the problems are treated at the many‐electron level. It has been found that the CFPs are transferable from one derivative to another, within a given series, as a first approximation. The sign of the second‐order parameter B02 differs in the two series, reflecting the different environments. It has been found that the use of the strength parameter S allows for an easy comparison between complexes. Furthermore, in both series, the parameters have been found to decrease in magnitude along the series, and this decrease is attributed to covalent effects.

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“…Probably, the primary approach which consists of considering only the point charge model might be oversimplified. Some authors pointed out with a deeper analysis that dipole and quadrupole moments in the electrostatic potential expansion play a significant role on the magnetic anisotropy[67,68].…”

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Tetrathiafulvalene-Based Magnets of Lanthanides

Cador

Pointillart

2018

Topics in Organometallic Chemistry

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Introduction 30 Magnets have been discovered about four millenniums ago in ancient Greece. 31 Nowadays, in 2015, permanent magnets market is valued to 15 billion € and is 32 expected to grow according to the demands for medical and industrial devices. In 33 this market, the segment occupied by the badly named rare-earth 1-based magnets 34 continues to expand owing to superior properties (such as saturation magnetization). 35 In the 1990s, a new class of magnets emerged in the scientific community with the discovery of the single-molecule magnets (SMMs) [1]. In these magnets, the magnetic memory is stored by the magnetic moment of a single molecule constituted of 12 manganese ions. This scientific finding reduced the size of a storage unit (byte) to nanometer. At the same time, the storage capacity of hard disks based on molecules would increase drastically. The drawback is the operating temperature range, below liquid helium (À269 C). In the last three decades, the quest for better SMMs never really stopped. In 2003, Ishikawa et al. [2] discovered that a single lanthanide ion (Ln ¼ Tb III) embedded in a doubledecker complex behaved as a SMM. To date, the lanthanide series is the most productive SMMs line in Mendeleev's periodic table with a recent tremendous record of closure of the magnetic hysteresis loop at 60 K [3, 4], close to liquid nitrogen. 47 Tetrathiafulvalene (TTF) and its analogues are well known in the field of molec-48 ular materials to produce organic metals, semiconductors, and superconductors 49 [5, 6]. The functionalization of the electron donor TTF core by an acceptor moiety 50 contributed to the development of functional materials such as switches, sensors, 51 photovoltaic cells, and nonlinear optical systems [7-9]. It was then logical to adapt 52 the acceptor moiety to coordinate transition metals for (1) elaboration of 53 multifunctional materials with both paramagnetism and electrical conductivity 54 [10, 11] and (2) the synthesis of polynuclear transition metal complexes exhibiting 55 SMM properties embedded in a conducting material [12-16]. One must admit that 56 all tentative proposals were not very successful except Oshio's work [17] which 57 shows SMM behavior but without conductivity.

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Magnetic Slow Relaxation in a Metal–Organic Framework Made of Chains of Ferromagnetically Coupled Single‐Molecule Magnets

Cited by 74 publications

References 145 publications

Covalency and magnetic anisotropy in lanthanide single molecule magnets: the DyDOTA archetype

Covalency and magnetic anisotropy in lanthanide single molecule magnets: the DyDOTA archetype

Derivation of Lanthanide Series Crystal Field Parameters From First Principles

Tetrathiafulvalene-Based Magnets of Lanthanides

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