Field-induced slow magnetic relaxation in the first Dy(<scp>iii</scp>)-centered 12-metallacrown-4 double-decker

Athanasopoulou, Angeliki A.; Baldoví, José J.; Carrella, Luca M.; Rentschler, Eva

doi:10.1039/c9dt02432h

Cited by 19 publications

(9 citation statements)

References 42 publications

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“…Metallacrown and metallacryptate chemistry has mainly focused on incorporating transition metal ions in the ring repeating unit as these ions impart interesting magnetic and spectroscopic properties. The use of main-group metal ions has mainly been limited to gallium (Lah et al, 1993;Jiang et al, 2019;Athanasopoulou et al, 2019), tellurium (Kü bel et al, 2010;Ho et al, 2016;Ho et al, 2017;Ho et al, 2019;Wang et al, 2019), and tin (Zhao et al, 2010a;Zhao et al, 2010b). Recently though, gallium-based metallacrowns and metallacryptates have gained renewed interest as potential optical imaging agents (Chow et al, 2016;Nguyen et al, 2018;Lutter et al, 2018Lutter et al, , 2019Lutter et al, , 2020.…”

Section: Chemical Contextmentioning

confidence: 99%

Crystal structures of two dysprosium–aluminium–sodium [3.3.1] metallacryptates that form two-dimensional sheets

et al. 2020

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The two [3.3.1] metallacryptate complexes, namely, poly[[μ3-acetato-hexakis(μ-N,N-dimethylformamide)bis(N,N-dimethylformamide)bis[salicylhydroximato(2−)]heptakis[salicylhydroximato(3−)]hexaaluminium(III)dysprosium(III)pentasodium(I)] N,N-dimethylformamide tetrasolvate monohydrate], [DyAl6Na5(OAc)(Hshi)2(shi)7(DMF)8]·4DMF·H2O or {[DyAl6Na5(C7H5NO3)2(C7H4NO3)7(C2H3O2)(C3H7NO)8]·4C3H7NO·H2O} n , 1, and poly[[di-μ4-acetato-nonakis(μ-N,N-dimethylformamide)octakis(N,N-dimethylformamide)tetrakis[salicylhydroximato(2-)]tetradecakis[salicylhydroximato(3−)]dodecaaluminium(III)didysprosium(III)decasodium(I)] N,N-dimethylformamide 6.335-solvate], [DyAl6Na5(OAc)(Hshi)2(shi)7(DMF)8.5]2·6.335DMF or {[Dy2Al12Na10(C7H5NO3)4(C7H4NO3)14(C2H3O2)2(C3H7NO)17]·6.335C3H7NO} n , 2, where shi3− is salicylhydroximate and DMF is N,N-dimethylformamide, both consist of an aluminium-based metallacryptand. In 1 and 2, the metallacryptand encapsulates a dysprosium(III) ion in the central cavity, and the resulting metallacryptates are connected to each other via sodium-DMF linkages to generate a two-dimensional sheet. The metallacryptates of 1 and 2 are the three-dimensional analogues of metallacrowns as the metallacryptates contain a metal–nitrogen–oxygen cyclic repeat unit throughout the complexes. For 1 the building block of the two-dimensional sheet is comprised of only one type of metallacryptate, which is connected to four neighboring metallacryptates via four sodium–DMF linkages. In 2, the building block is a dimeric unit of two metallacryptates. Each dimeric metallacryptate unit is connected to four other dimeric units via six sodium–DMF linkages. The two metallacryptates of each dimeric unit can be considered enantiomers of each other. In both 1 and 2, chirality is imparted to the metallacryptate due to the Λ and Δ propeller configurations of the four octahedral aluminium ions of the metallacryptand shell.

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Section: Chemical Contextmentioning

confidence: 99%

Crystal structures of two dysprosium–aluminium–sodium [3.3.1] metallacryptates that form two-dimensional sheets

et al. 2020

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“…Unlike other high-performing SMMs, metallacrowns show a high stability in air and in solution and can be synthesized by a self-assembly approach. Lanthanide-centered half-sandwich and sandwich-type metallacrown complexes with ring ions like Al 3+ , Fe 3+ , Ga 3+ , Mn 3+ , and Zn 2+ have been synthesized to study their luminescent and magnetic properties. − However, although the reported complexes possess D 4 d symmetry, the energy barrier is considerably low. ,− For Tb 3+ complexes, a closer look at the ideal ligand-field conditions reveals that the anisotropy is highly dependent on the zenithal angle α (Figure ).…”

Section: Introductionmentioning

confidence: 99%

3d/4f Sandwich Complex Based on Metallacrowns

et al. 2021

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A novel lanthanide double-decker complex with nickel metallacrowns (MCs) as coordinating ligands has been synthesized. In the 3d/4f metallacrown complex TbIII[12-MCNiIIN(shi)-4]2, the central lanthanide ion is sandwiched between two [12-MC-4] units, forming an almost ideal square-antiprismatic coordination sphere. The resulting zenithal angles at the central lanthanide ion are smaller than those for previously reported sandwich compounds. Magnetic measurements reveal an energy barrier of 346 K under zero field and up to 585 K under 3200 Oe, the highest reported for metallacrowns with D 4d symmetry.

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“…We should note that a Ga 3+ /Dy 3+ MC possessing a molecular geometry, which shares structural similarities to Ln-1 but which is formed with another counter-cation (n-Bu 4 N + vs Na + ), was obtained through a different synthetic route and was independently reported by the Rentschler group in a recent communication focused exclusively on single molecule magnet properties. 71 Luminescence properties were not described in that publication. It is important to note that we have previously evidenced that the nature of the counter-cation in the MC structure may significantly affect photophysical properties.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The present structure is also the first MC in which efficient sensitization of red Eu 3+ emission occurs. We should note that a Ga 3+ /Dy 3+ MC possessing a molecular geometry, which shares structural similarities to Ln-1 but which is formed with another counter-cation (n-Bu 4 N + vs Na + ), was obtained through a different synthetic route and was independently reported by the Rentschler group in a recent communication focused exclusively on single molecule magnet properties . Luminescence properties were not described in that publication.…”

Section: Introductionmentioning

confidence: 99%

Visible, Near-Infrared, and Dual-Range Luminescence Spanning the 4f Series Sensitized by a Gallium(III)/Lanthanide(III) Metallacrown Structure

et al. 2020

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Lanthanide(III) ions (Ln 3+ ) in coordination compounds exhibit unique luminescent properties with narrow and characteristic f-f transitions throughout the visible and near-infrared (NIR) ranges. In addition, some Ln 3+ such as Pr 3+ , Sm 3+ , Dy 3+ , Ho 3+ , Er 3+ and Tm 3+ possess an exceptional ability, although less explored, to exhibit dual-range emissions. Such remarkable features allow highly specific use in materials sciences and biology, for example, for the creation of sophisticated barcode modules or for the next generation of optical imaging applications. Herein, a series of Ga 3+ /Ln 3+ metallacrowns (MCs) with the general composition [LnGa8(shi)8(OH)4]Na•xCH3OH•yH2O (Ln-1, Ln = Pr 3+ , Nd 3+ , Sm 3+ -Yb 3+ and analogue Y 3+ ; H3shi = salicylhydroxamic acid) is presented. Ln-1 were obtained by reacting Ga 3+ and Ln 3+ nitrate salts with the H3shi ligand. X-ray single crystal unit cell analysis confirmed that all MCs are isostructural. The crystal structure was solved for the Nd 3+ analogue and revealed that Nd 3+ is centered between two [12-MCGa III N(shi)-4] MC rings and bound to eight hydroximate oxygen ions (four from each ring) in a pseudo-square antiprismatic fashion adopting a pseudo-D4h symmetry. PGSE DOSY 1 H NMR spectroscopy and ESI mass-spectrometry confirmed that the structure of Ln-1 remains intact in methanol solutions while mass spectrometry suggests that four OHbridges are exchanged with CH3O -/CD3O -. An exceptional ability of this series of MCs to sensitize the characteristic emission of Ln 3+ was confirmed with the observation of bright red and green emission signals of Eu-1 and Tb-1, NIR emissions of Yb-1 and Nd-1, and dual-range emissions of Pr-1, Sm-1, Dy-1, Ho-1, Er-1 and Tm-1 in the solid state upon excitation into ligand-centered bands at 340 nm. The luminescence properties of Ln-1 (Ln = Nd 3+ , Sm 3+ , Eu 3+ , Tb 3+ , Dy 3+ , Yb 3+ ) were also investigated in CH3OH and CD3OD solutions. For Eu-1 and Yb-1 MCs, more extensive analyses of the photophysical properties were performed that included the determination of radiative lifetimes, intrinsic quantum yields and sensitization efficiencies. The absolute quantum yields ( ) of Ln-1 in the visible and in the NIR ranges have been determined. In the case of Sm-1 the values of in CH3OH and CD3OD solutions are exceptionally high, i.e. 10.1(5) % and 83(1) %. Values obtained for Yb-1, i.e. 0.78(4) % in CH3OH and 8.4(1)% in CD3OD, are among the highest ones reported today for Yb 3+ complexes formed with non-deuterated and non-halogenated ligands.Absorption spectra. Absorption spectra (Figure S9) were collected on freshly prepared 50 µM solutions of Ln-1 in methanol (Merck, Uvasol®) placed in quartz cuvettes on a Jasco V670 UV-visible spectrophotometer in absorbance mode.Synthesis and characterization. All reagents and chemicals were purchased from commercial sources and used without further purification. All reactions were carried out aerobically under ambient conditions. Elemental analysis was performed by Atlantic Microlabs Inc. ESI-M...

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Field-induced slow magnetic relaxation in the first Dy(iii)-centered 12-metallacrown-4 double-decker

Abstract: The first double-decker Ga(iii)/Dy(iii) 12-MC-4 complex has been isolated and magnetic studies revealed its SMM properties.

Cited by 19 publications

References 42 publications

Crystal structures of two dysprosium–aluminium–sodium [3.3.1] metallacryptates that form two-dimensional sheets

Crystal structures of two dysprosium–aluminium–sodium [3.3.1] metallacryptates that form two-dimensional sheets

3d/4f Sandwich Complex Based on Metallacrowns

Visible, Near-Infrared, and Dual-Range Luminescence Spanning the 4f Series Sensitized by a Gallium(III)/Lanthanide(III) Metallacrown Structure

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