Teaching an old molecule new tricks: evidence and rationalisation of the slow magnetisation dynamics in [DyTp<sub>2</sub>Acac]

Guégan, Frédéric; Riobé, François; Maury, Olivier; Jung, Jaehun; Guennic, Boris Le; Morell, Christophe; Luneau, Dominique

doi:10.1039/c8qi00174j

Cited by 15 publications

(11 citation statements)

References 61 publications

(77 reference statements)

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“…There is considerable interest in the discovery of new lanthanide (Ln)-containing materials due to their unique, intrinsic magnetic and photophysical properties and the desire to design functional Ln materials for specific applications. , This is typically achieved via the judicious choice of an organic ligand with desirable properties, to generate hybrid (organic–inorganic) materials, where the ligand can influence which lanthanide property(ies) is(are) expressed. In particular, lanthanide complexes with pyrazolylborate ligands are of interest to researchers as they display single molecule magnet properties − and sensitized Ln 3+ emission , as well as C–H activation catalysis. − Lanthanide pyrazolylborate complexes, despite their promising chemical and physical properties, are still relatively underexplored, with only a limited range of pyrazolylborates used. , …”

Section: Introductionmentioning

confidence: 99%

Structural Diversity of Lanthanide 3-Nitrotrispyrazolylborates: Tunable Nuclearity and Intra-Ligand Charge Transfer Sensitization of Visible and NIR Ln³⁺ Emission

et al. 2021

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Reported are the syntheses, crystal structures, and photophysical properties of 28, novel lanthanide compounds across five structural types, [Ln(3-NO2Tp)2(NO3)] (1-Ln, Ln = La–Tm, except Pm), [Bu4N][Ln(3-NO2Tp)(NO3)3] (2-Ln, Ln = Yb, Lu), [Eu(3-NO2Tp)2Cl(H2O)]·2 i PrOH (3-Eu), [{Ln(3-NO2Tp)2}2(μ2-CO3)]·MeOH (4-Ln, Ln = La–Gd, except Pm), and [{Ln(3-NO2Tp)}4(μ2-OMe)6(μ4-O)] (5-Ln, Ln = Pr–Tb, except Pm) with the 3-nitrotrispyrazolylborate (3-NO2Tp–) ligand. The reaction of methanol or isopropanol solutions of LnX3 (X = Cl, NO3) with the tetrabutyl ammonium salt of the flexidentate 3-NO2Tp– ([Bu4N][3-NO2Tp]) yields Ln(3-NO2Tp) x complexes of various nuclearities as either monomers (1-Ln, 2-Ln, 3-Eu), dimers (4-Ln), or tetramers (5-Ln) owing to the efficient conversion of atmospheric CO2 to CO3 2– (dimers) or ligand controlled solvolysis of lanthanide ions (tetramers). 3-NO2Tp– is an efficient sensitizer for both the visible and near-IR (NIR) emissions of most of the lanthanide series, except thulium. Optical measurements, supported by density functional theory calculations, indicate that the dual visible and NIR Ln3+ emission arises from two intraligand charge transfer (ILCT) transitions of 3-NO2Tp–. This is the first report of lanthanide complexes with a nitro-functionalized pyrazolylborate ligand. The derivatization of the known Tp– ligand results in new coordination chemistry governed by the increased denticity of 3-NO2Tp–, imparting remarkable structural diversity and charge transfer properties to resultant lanthanide complexes.

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Section: Introductionmentioning

confidence: 99%

Structural Diversity of Lanthanide 3-Nitrotrispyrazolylborates: Tunable Nuclearity and Intra-Ligand Charge Transfer Sensitization of Visible and NIR Ln³⁺ Emission

et al. 2021

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“…This empirical parameter is convenient to describe the temperature dependence of the relaxation time but provides no information about the underlying mechanisms leading to demagnetization. Multireference electronic structure calculations are commonly employed to gain further insight about the level spacing and magnetic anisotropy of SMMs. − In favorable cases, U eff can be connected with a specific excited state in a qualitative manner. However, there is no standard protocol to predict effective demagnetization barriers from ab initio data in a univocal way.…”

mentioning

confidence: 99%

Ab Initio Prediction of Tunneling Relaxation Times and Effective Demagnetization Barriers in Kramers Lanthanide Single-Molecule Magnets

Aravena

2018

J. Phys. Chem. Lett.

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Single-molecule magnets (SMMs) are promising candidates for molecule-based quantum information devices. Their main limitation is their cryogenic operative temperature. To achieve devices performing at higher temperatures, demagnetization mechanisms must be suppressed by chemical tuning. Electronic structure calculations can provide useful information to rationalize SMM behavior, but they do not provide a direct prediction for the key experimental parameters describing magnetic relaxation (i.e., tunneling relaxation time (τ) and effective demagnetization barrier ( U)). In this Letter, a first-principles model is proposed to predict τ and U for mononuclear, half-integer spin SMMs, allowing direct comparison with experiment. Model accuracy was assessed against experimental data for 18 mononuclear Ln complexes (15 Dy and 3 Er) and applied to 3 of the current best-performing SMMs, correctly predicting nontrivial relaxation pathways. The model shows that the combination of single-ion anisotropy and spin-spin dipolar coupling can account for the major part of tunneling demagnetization for the studied systems.

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“…The investigation of the luminescent properties of Ln-SMM [53] is now a common procedure to establish magneto-luminescent correlations [54]. However these have been mainly performed on Tb III and Dy III ions because of their efficient SMM behaviors coupled with good emission properties (see ref [54] for full review) [55][56][57][58][59]. The approach has been less developed on NIR emissive Ln-SMM where mainly Er III -SMM [60][61][62][63][64][65] and Yb III -SMM [29,[66][67][68][69][70][71][72][73] have been investigated.…”

Section: Luminescence Measurementsmentioning

confidence: 99%

Closing the Circle of the Lanthanide-Murexide Series: Single-Molecule Magnet Behavior and Near-Infrared Emission of the NdIII Derivative

et al. 2018

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Up to now, even if murexide-based complexometric studies are performed with all 3d or 4f ions, the crystal structures of the light-lanthanide derivatives of the lanthanide-murexide series are unknown. In this work, we report the crystal structure of the NdIII derivative named NdMurex. Contrary to all known complexes of the 3d or 4f series, a dimeric compound was obtained. As for its already reported DyIII and YbIII parents, the NdIII complex responsible for the color-change behaves as a single-molecule magnet (SMM). This behavior was observed on both the crystalline (NdMurex: Ueff = 6.20(0.80) K, 4.31 cm−1; τ0 = 2.20(0.92) × 10−5 s, Hdc = 1200 Oe) and anhydrous form (NdMurexAnhy: Ueff = 6.25(0.90) K, 4.34 cm−1; τ0 = 4.85(0.40) × 10−5 s, Hdc = 1200 Oe). The SMM behavior is reported also for the anhydrous CeIII derivative (CeMurexAnhy: Ueff = 5.40(0.75) K, 3.75 cm−1; τ0 = 3.02(1.10) × 10−5 s, Hdc = 400 Oe). The Near-Infrared Emission NIR emission was observed for NdMurexAnhy and highlights its bifunctionality.

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Teaching an old molecule new tricks: evidence and rationalisation of the slow magnetisation dynamics in [DyTp₂Acac]

Abstract: Combined analyses of magnetic and luminescence measurements, with the support of theoretical calculations, help elucidate the origin of [DyTp2Acac]'s SMM behaviour.

Cited by 15 publications

References 61 publications

Structural Diversity of Lanthanide 3-Nitrotrispyrazolylborates: Tunable Nuclearity and Intra-Ligand Charge Transfer Sensitization of Visible and NIR Ln³⁺ Emission

Structural Diversity of Lanthanide 3-Nitrotrispyrazolylborates: Tunable Nuclearity and Intra-Ligand Charge Transfer Sensitization of Visible and NIR Ln³⁺ Emission

Ab Initio Prediction of Tunneling Relaxation Times and Effective Demagnetization Barriers in Kramers Lanthanide Single-Molecule Magnets

Closing the Circle of the Lanthanide-Murexide Series: Single-Molecule Magnet Behavior and Near-Infrared Emission of the NdIII Derivative

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Teaching an old molecule new tricks: evidence and rationalisation of the slow magnetisation dynamics in [DyTp2Acac]

Abstract: Combined analyses of magnetic and luminescence measurements, with the support of theoretical calculations, help elucidate the origin of [DyTp2Acac]'s SMM behaviour.

Cited by 15 publications

References 61 publications

Structural Diversity of Lanthanide 3-Nitrotrispyrazolylborates: Tunable Nuclearity and Intra-Ligand Charge Transfer Sensitization of Visible and NIR Ln3+ Emission

Structural Diversity of Lanthanide 3-Nitrotrispyrazolylborates: Tunable Nuclearity and Intra-Ligand Charge Transfer Sensitization of Visible and NIR Ln3+ Emission

Ab Initio Prediction of Tunneling Relaxation Times and Effective Demagnetization Barriers in Kramers Lanthanide Single-Molecule Magnets

Closing the Circle of the Lanthanide-Murexide Series: Single-Molecule Magnet Behavior and Near-Infrared Emission of the NdIII Derivative

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Teaching an old molecule new tricks: evidence and rationalisation of the slow magnetisation dynamics in [DyTp₂Acac]

Structural Diversity of Lanthanide 3-Nitrotrispyrazolylborates: Tunable Nuclearity and Intra-Ligand Charge Transfer Sensitization of Visible and NIR Ln³⁺ Emission

Structural Diversity of Lanthanide 3-Nitrotrispyrazolylborates: Tunable Nuclearity and Intra-Ligand Charge Transfer Sensitization of Visible and NIR Ln³⁺ Emission