Dy3+ White Light Emission Can Be Finely Controlled by Tuning the First Coordination Sphere of Ga3+/Dy3+ Metallacrown Complexes

Eliseeva, Svetlana V.; Salerno, Elvin V.; Bermudez, Beatriz A. Lopez; Petoud, Stéphane; Pecoraro, Vincent L.

doi:10.1021/jacs.0c07198

Cited by 33 publications

(31 citation statements)

References 27 publications

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“…These are expected to generate distinct single-ion anisotropy and better magnetic isolation within the crystal lattice 81 – 83 . We decided to explore Dy(III) complexes which are yellow-to-white emissive as a result of the characteristic f-f electronic transitions 25 , 84 , and found to be highly anisotropic in diverse coordination environments.…”

Section: Introductionmentioning

confidence: 99%

Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets

Wegner

Zakrzewski

Żychowicz

et al. 2021

Sci Rep

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Luminescent single-molecule magnets (SMMs) constitute a class of molecular materials offering optical insight into magnetic anisotropy, magnetic switching of emission, and magnetic luminescent thermometry. They are accessible using lanthanide(III) complexes with advanced organic ligands or metalloligands. We present a simple route to luminescent SMMs realized by the insertion of well-known organic cations, tetrabutylammonium and tetraphenylphosphonium, into dysprosium(III) borohydrides, the representatives of metal borohydrides investigated due to their hydrogen storage properties. We report two novel compounds, [n-Bu4N][DyIII(BH4)4] (1) and [Ph4P][DyIII(BH4)4] (2), involving DyIII centers surrounded by four pseudo-tetrahedrally arranged BH4– ions. While 2 has higher symmetry and adopts a tetragonal unit cell (I41/a), 1 crystallizes in a less symmetric monoclinic unit cell (P21/c). They exhibit yellow room-temperature photoluminescence related to the f–f electronic transitions. Moreover, they reveal DyIII-centered magnetic anisotropy generated by the distorted arrangement of four borohydride anions. It leads to field-induced slow magnetic relaxation, well-observed for the magnetically diluted samples, [n-Bu4N][YIII0.9DyIII0.1(BH4)4] (1@Y) and [Ph4P][YIII0.9DyIII0.1(BH4)4] (2@Y). 1@Y exhibits an Orbach-type relaxation with an energy barrier of 26.4(5) K while only the onset of SMM features was found in 2@Y. The more pronounced single-ion anisotropy of DyIII complexes of 1 was confirmed by the results of the ab initio calculations performed for both 1–2 and the highly symmetrical inorganic DyIII borohydrides, α/β-Dy(BH4)3, 3 and 4. The magneto-luminescent character was achieved by the implementation of large organic cations that lower the symmetry of DyIII centers inducing single-ion anisotropy and separate them in the crystal lattice enabling the emission property. These findings are supported by the comparison with 3 and 4, crystalizing in cubic unit cells, which are not emissive and do not exhibit SMM behavior.

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Section: Introductionmentioning

confidence: 99%

Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets

Wegner

Zakrzewski

Żychowicz

et al. 2021

Sci Rep

View full text Add to dashboard Cite

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“…All these potential applications requires highly emissive materials and therefore the quest for new lanthanide-based coordination compounds exhibiting bright luminescence constitutes a continuous concern. [21][22][23][24][25][26][27][28] The strategy that consists on focusing on the choice of the ligand is, by far, the most commonly followed. [15][16][29][30] The works along this line have demonstrated that the ligands must present a structuring effect (via -stacking interactions, hydrogen-or halogen-bonds), an efficient antenna effect 31 and a good chemical affinity toward lanthanide ions.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Crystal Structure, and Luminescence Properties of the Iso-Reticular Series of Lanthanide Coordination Polymers Synthesized from Hexa-Lanthanide Molecular Precursors

et al. 2022

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“…The organic molecule N ,2-dihydroxybenzamide (H 2 dihybe) ( Scheme 1 A) incorporates a hydroxamate group in addition to the phenoxy group in the ortho-position and exhibits a rich coordination chemistry with many transition metals [ 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 ] with potential applications in various fields ranging from medicine [ 41 , 42 , 43 ] to materials [ 44 ], and physical sciences [ 40 , 45 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structural and Physicochemical Characterization of a Titanium(IV) Compound with the Hydroxamate Ligand N,2-Dihydroxybenzamide

et al. 2021

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The siderophore organic ligand N,2-dihydroxybenzamide (H2dihybe) incorporates the hydroxamate group, in addition to the phenoxy group in the ortho-position and reveals a very rich coordination chemistry with potential applications in medicine, materials, and physical sciences. The reaction of H2dihybe with TiCl4 in methyl alcohol and KOH yielded the tetranuclear titanium oxo-cluster (TOC) [TiIV4(μ-O)2(HOCH3)4(μ-Hdihybe)4(Hdihybe)4]Cl4∙10H2O∙12CH3OH (1). The titanium compound was characterized by single-crystal X-ray structure analysis, ESI-MS, 13C, and 1H NMR spectroscopy, solid-state and solution UV–Vis, IR vibrational, and luminescence spectroscopies and molecular orbital calculations. The inorganic core Ti4(μ-O)2 of 1 constitutes a rare structural motif for discrete TiIV4 oxo-clusters. High-resolution ESI-MS studies of 1 in methyl alcohol revealed the presence of isotopic distribution patterns which can be attributed to the tetranuclear clusters containing the inorganic core {Ti4(μ-O)2}. Solid-state IR spectroscopy of 1 showed the presence of an intense band at ~800 cm−1 which is absent in the spectrum of the H2dihybe and was attributed to the high-energy ν(Ti2–μ-O) stretching mode. The ν(C=O) in 1 is red-shifted by ~10 cm−1, while the ν(N-O) is blue-shifted by ~20 cm−1 in comparison to H2dihybe. Density Functional Theory (DFT) calculations reveal that in the experimental and theoretically predicted IR absorbance spectra of the ligand and Ti-complex, the main bands observed in the experimental spectra are also present in the calculated spectra supporting the proposed structural model. 1H and 13C NMR solution (CD3OD) studies of 1 reveal that it retains its integrity in CD3OD. The observed NMR changes upon addition of base to a CD3OD solution of 1, are due to an acid–base equilibrium and not a change in the TiIV coordination environment while the decrease in the complex’s lability is due to the improved electron-donating properties which arise from the ligand deprotonation. Luminescence spectroscopic studies of 1 in solution reveal a dual narrow luminescence at different excitation wavelengths. The TOC 1 exhibits a band-gap of 1.98 eV which renders it a promising candidate for photocatalytic investigations.

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Dy³⁺ White Light Emission Can Be Finely Controlled by Tuning the First Coordination Sphere of Ga³⁺/Dy³⁺ Metallacrown Complexes

Cited by 33 publications

References 27 publications

Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets

Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets

Synthesis, Crystal Structure, and Luminescence Properties of the Iso-Reticular Series of Lanthanide Coordination Polymers Synthesized from Hexa-Lanthanide Molecular Precursors

Synthesis, Structural and Physicochemical Characterization of a Titanium(IV) Compound with the Hydroxamate Ligand N,2-Dihydroxybenzamide

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