Recent advances in luminescent lanthanide based Single-Molecule Magnets

Long, Jérôme; Guari, Yannick; Ferreira, Rute A. S.; Carlos, Luı́s D.; Larionova, Joulia

doi:10.1016/j.ccr.2018.02.019

Cited by 237 publications

(149 citation statements)

References 161 publications

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“…53,[90][91][92][93] Since then magneto-luminescent correlations flourished. 94 Low temperature (77 K) solid state luminescence spectra measured on a single-crystal of Tb-TEMPO-CN are provided in Figure 7. The excitation spectrum highlights a broad band below 330 nm that is attributed to π*(hfac) → π(hfac) transitions.…”

Section: Magneto-luminescent Correlationsmentioning

confidence: 99%

Strong Magnetic Coupling and Single-Molecule-Magnet Behavior in Lanthanide-TEMPO Radical Chains

et al. 2018

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The rational design of molecular chains made of 4f ions and substituted 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical is presented. The reaction of Ln(hfac)·2HO (hfac = hexafluoroacetylacetonate) and the 4-cyano-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO-CN) radical affords air- and moisture-stable isostructural molecular chains of the formula [Ln(hfac)TEMPO-CN] for Ln = Gd and Tb, whereas zero-dimensional complexes of the formula [Dy(hfac)(TEMPO-CN)][Dy(hfac)(HO)] are obtained for Ln = Dy. To the best of our knowledge, the Gd derivative, Gd-TEMPO-CN, shows one of the strongest antiferromagnetic (AF) couplings for Gd-radical pairs ever reported with J/ k = -21.18 K, 14.72 cm ( H = - JS S spin Hamiltonian convention). The Tb derivative, Tb-TEMPO-CN, also shows strong Tb-radical AF coupling, which has been rationalized using the ab initio CASSCF approach ( J = -23.02 K, -16.7 cm) and confirmed by luminescence measurements. Tb-TEMPO-CN shows remarkable properties for a Tb-radical-based single-molecule magnet ( U = 69.3 ± 1 K; τ = 1.3 × 10 s) and two different relaxation processes triggered by interchain magnetic coupling.

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Section: Magneto-luminescent Correlationsmentioning

confidence: 99%

Strong Magnetic Coupling and Single-Molecule-Magnet Behavior in Lanthanide-TEMPO Radical Chains

et al. 2018

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“…Some of us and other groups contributed to the revival of this old idea and in the beginning of the 2010s established correlation between magnetism and luminescence on Dy III -a nd also Yb III -based SMMs. [19][20][21][22][23][24][25][26] These results triggered anew interest into high-resolution luminescence measurements in order to experimentally establish the complete diagram of luminescentS MMs. Althoughc lassical,s uch determination can be quite tricky because of the presence of "extra-transitions"i nt he luminescence spectra,a ssigned sometimes too rapidlyt o" hot bands" or vibronic transitions [3,27,28] (see also ref.…”

Section: Introductionmentioning

confidence: 99%

Luminescence‐Driven Electronic Structure Determination in a Textbook Dimeric Dy^III‐Based Single‐Molecule Magnet

Guettas

Gendron

Garcia

et al. 2020

Chemistry A European J

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A textbook dysprosium dinuclear complex based on acetylacetone ligands, [Dy2(acac)4(μ2‐acac)2(H2O)2], has been synthesized and fully characterized. This simple dimeric lanthanide complex shows well‐resolved solid‐state luminescence and behaves as a single‐molecule magnet under zero DC field. A seminal crystal‐field approach is used to marry both magnetism and luminescence in the frame of an energetic picture.

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“…The luminescence of trivalent lanthanide ions (Ln 3+ ) has been received much attention in diverse applications ranging from the development of advanced optical and light‐converting devices to bio‐imaging, single‐ion magnets, and theragnostic . Specifically, Eu 3+ ions exhibit compelling photophysical properties such as easily recognizable sharp emission bands (< 10 nm), long excited‐state lifetimes (> 0.1 ms), and ligand‐induced large Stokes shifts , …”

Section: Introductionmentioning

confidence: 99%

Efficient Visible‐Light‐Excitable Eu³⁺ Complexes for Red Organic Light‐Emitting Diodes

et al. 2020

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Visible-light-excited Eu 3+ complexes have received much attention in the last years due to the rapidly increasing demand for less-harmful biomarkers and low-voltage driven emitters in optoelectronics. Nevertheless, these complexes usually exhibit poor emission quantum yields, contrarily to the ones excited in the ultraviolet spectral region. To address this challenge, a series of complexes based on trivalent lanthanide ions, [Eu(bpyO2)(2), Gd (5)} and Ln(tta) 3 (bpyO2) {Ln = Eu (3), Gd (6)}, were synthesized using 2-thenoyltrifluoroacetone (Htta) as primary ligand and 2,2′-dipyridyl N,N′-dioxide (bpyO2) as neutral donor, and characterized, with special emphasis on their crystal struc-[a] Phantom-g, CICECO -was achieved through chemical modifications of the ligand structure with an expanded π-conjugated system [40] and using either neutral tris-(Q Ln L = 0.75 at 415 nm [49] and 0.40 at 400 nm [46] ) or anionic tetrakis-Eu 3+ --diketonates (Q Ln L = 0.80 at 410 nm [40] and Q Ln L = 0.45 at 400 nm [48] ).In this work, we followed a rational design to synthesize three Eu 3+ --diketonate complexes, 1, 2 and 3, using 2-thenoyltrifluoroacetone (Htta) and 2,2′-dipyridyl N,N′-dioxide (bpyO2) as the primary and ancillary ligands, respectively. The excitation window of 3 unprecedently extends into the visible region (up to 480 nm), well-above what was reported previously for analogous visible-light-excitable Eu 3+ -based complexes (up to 440-450 nm). [40,46,48] Detailed theoretical calculations performed with both time-dependent density functional theory (TD-DFT) and LUMPAC software [51] are also presented showing an excellent accord with the experimental intensity parameters, radiative and non-radiative decay rates, and intrinsic and absolute emission quantum yields. Moreover, 3 displayed excellent colour purity, with Commission Internationale d'Éclairage (CIE) chromaticity coordinates (0.66, 0.33), and was successfully employed for the fabrication of organic light-emitting diodes (OLEDs). Results and DiscussionScheme 1 summarizes the adopted synthesis procedure. Complexes 1-3 were characterized using ATR/FT-IR spectroscopy, mass spectrometry, and elemental analyses. In the FT-IR spectra, the stretching and bending vibrations of N-O group of bpyO2 ligand are observed in 1 (1260, 853 and 837 cm -1 ) and 3 (1255, 856 and 836 cm -1 ) ( Figure S1). The carbonyl stretching frequency of Htta has been shifted from 1645 cm -1 to 1600 and 1, 2, 3, 4, and 6 were analysed by singlecrystal XRD. The most relevant structural features of 1-3 are depicted in Figure 1 and those of 4 and 6 are given in Figure S3 and S4, respectively. Selected bond lengths and bond angles Eur. Single-Crystal X-ray Structures Suitable crystals of

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Recent advances in luminescent lanthanide based Single-Molecule Magnets

Cited by 237 publications

References 161 publications

Strong Magnetic Coupling and Single-Molecule-Magnet Behavior in Lanthanide-TEMPO Radical Chains

Strong Magnetic Coupling and Single-Molecule-Magnet Behavior in Lanthanide-TEMPO Radical Chains

Luminescence‐Driven Electronic Structure Determination in a Textbook Dimeric Dy^III‐Based Single‐Molecule Magnet

Efficient Visible‐Light‐Excitable Eu³⁺ Complexes for Red Organic Light‐Emitting Diodes

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Recent advances in luminescent lanthanide based Single-Molecule Magnets

Cited by 237 publications

References 161 publications

Strong Magnetic Coupling and Single-Molecule-Magnet Behavior in Lanthanide-TEMPO Radical Chains

Strong Magnetic Coupling and Single-Molecule-Magnet Behavior in Lanthanide-TEMPO Radical Chains

Luminescence‐Driven Electronic Structure Determination in a Textbook Dimeric DyIII‐Based Single‐Molecule Magnet

Efficient Visible‐Light‐Excitable Eu3+ Complexes for Red Organic Light‐Emitting Diodes

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Product

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Luminescence‐Driven Electronic Structure Determination in a Textbook Dimeric Dy^III‐Based Single‐Molecule Magnet

Efficient Visible‐Light‐Excitable Eu³⁺ Complexes for Red Organic Light‐Emitting Diodes