Metallacrowns: Supramolecular Constructs With Potential in Extended Solids, Solution-State Dynamics, Molecular Magnetism, and Imaging

Lutter, Jacob C.; Zaleski, Curtis M.; Pecoraro, Vincent L.

doi:10.1016/bs.adioch.2017.11.007

Cited by 21 publications

(21 citation statements)

References 156 publications

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“…(MCs) constitute a class of supramolecular complexes which possess a [M-N-O]n repeating ring motif. [1][2] The M n+ ring cations are usually 3d transition metal ions (from vanadium(V) to zinc(II)), but MCs with the group 13 triels such as gallium(III) [3][4][5][6] or with 4d and 5d transition metal ions (e.g. palladium(II), platinum(II)) 7 have also been synthesized.…”

Section: Metallacrownsmentioning

confidence: 99%

“…[28][29] It has been shown that many MCs are able to bind a single or multiple trivalent lanthanide(III) ions (Ln 3+ ). 1 Ln 3+ are widely studied for their unique optical properties derived from core-like valence 4f orbitals. Since 4f orbitals are present within the 5s and 5p orbitals, they are largely shielded from crystal field and covalent bonding effects.…”

Section: Metallacrownsmentioning

confidence: 99%

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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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Section: Metallacrownsmentioning

confidence: 99%

Section: Metallacrownsmentioning

confidence: 99%

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

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“…In this regard, we have adapted the synthetic procedure for 1,2,5oxadiazole with amino-and hydroxamate groups in the 4-and 3-position of the 1,2,5-oxadiazole ring, respectively, and report here the thallium(I) salt of this compound, 1, Tl(C 3 H 3 N 4 O 3 ). The introduction of a hydroxamic group at the 1,2,5-oxadiazole ring allows the consideration of potentially interesting ligand systems for the synthesis of various polynuclear complexes (Pavlishchuk et al, 2018;Lutter et al, 2018;Ostrowska et al, 2019;Gumienna-Kontecka et al, 2007).…”

Section: Chemical Contextmentioning

confidence: 99%

Crystal structure of poly[(μ₃-4-amino-1,2,5-oxadiazole-3-hydroxamato)thallium(I)]

et al. 2020

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The title compound represents the thallium(I) salt of a substituted 1,2,5-oxadiazole, [Tl(C3H3N4O3)] n , with amino- and hydroxamate groups in the 4- and 3- positions of the oxadiazole ring, respectively. In the crystal, the deprotonated hydroxamate group represents an intermediate between the keto/enol tautomers and forms a five-membered chelate ring with the thallium(I) cation. The coordination sphere of the cation is augmented to a distorted disphenoid by two monodentately binding O atoms from two adjacent anions, leading to the formation of zigzag chains extending parallel to the b axis. The cohesion within the chains is supported by π–π stacking [centroid–centroid distance = 3.746 (3) Å] and intermolecular N—H...N hydrogen bonds.

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“…Each of the presented MCs shares a common 12metallacrown-4 motif based on diamagnetic Ga 3+ ring metals and salicylhydroxamic acid (H 3 shi) ring ligands, [12-MC Ga III N(shi) -4]; 15,16 (3), 19 [DyGa 8 (shi) 8 (OH) 4 ]Na ( 4) 20 (bz − = benzoate, pyH + = pyridinium, ip 2− = isophthalate). In addition, the novel MC [DyGa 4 (shi) 4 (bz) 4 ]Na (5) has been synthesized and fully characterized (Figure 1, Scheme S1).…”

mentioning

confidence: 99%

“…Each of the presented MCs shares a common 12-metallacrown-4 motif based on diamagnetic Ga 3+ ring metals and salicylhydroxamic acid (H 3 shi) ring ligands, [12-MC Ga III N(shi) -4]; , however, the geometry about the Dy 3+ and the counter cations balancing charges in the structures are varied. Four MCs that we have previously described are newly analyzed for WLE: [DyGa 4 (shi) 4 (bz) 4 ](pyH) ( 1 ), [DyGa 4 (shi) 4 (H 2 shi) 2 (NO 3 )] ( 2 ), [Dy 2 Ga 8 (shi) 8 (ip) 4 ](NH 4 ) 2 ( 3 ), [DyGa 8 (shi) 8 (OH) 4 ]Na ( 4 ) (bz – = benzoate, pyH + = pyridinium, ip 2– = isophthalate).…”

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

et al. 2020

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Single lanthanide(III) ion white light emission is in high demand since it provides the advantage of requiring only one chromophore for the control of the color. Herein, a series of Ga3+/Dy3+ metallacrowns (MCs) is presented, demonstrating outstanding white light colorimetric properties with CIE chromaticity coordinates of (0.309, 0.334) and correlated color temperature (CCT) equal to 6670 K for the MC emitting the closest to the standard white color. Experimental data reveal that the CIE coordinates within the studied series of MCs are controlled mainly by the Dy3+-centered emission rather than by the ligand-centered bands, implying that Dy3+ can be tuned as a single ionic white light emitter by a simple modification of the coordination environment.

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Metallacrowns: Supramolecular Constructs With Potential in Extended Solids, Solution-State Dynamics, Molecular Magnetism, and Imaging

Cited by 21 publications

References 156 publications

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

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

Crystal structure of poly[(μ₃-4-amino-1,2,5-oxadiazole-3-hydroxamato)thallium(I)]

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

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Metallacrowns: Supramolecular Constructs With Potential in Extended Solids, Solution-State Dynamics, Molecular Magnetism, and Imaging

Cited by 21 publications

References 156 publications

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

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

Crystal structure of poly[(μ3-4-amino-1,2,5-oxadiazole-3-hydroxamato)thallium(I)]

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

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Crystal structure of poly[(μ₃-4-amino-1,2,5-oxadiazole-3-hydroxamato)thallium(I)]

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