Self-assembly and luminescence of trinuclear lanthanide based supramolecular circular helicates

Chang, Fei‐Fan; Feng, Fan-Da; Geng, Jiao; Huang, Wei

doi:10.1039/d1cc03376j

Cited by 7 publications

(9 citation statements)

References 24 publications

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“…Slight differences in the lengths of the M–O bonds in compounds 3 , 4 , and 5 result from the different lengths of the ionic radii of the lanthanide cations. These values correspond to the length of the M–O bonds found in the compounds Eu, Dy, and Er described by Huang et al and Tb, Dy, Ho, and Er reported by Li et al, which contain M–O–Ph fragments.…”

Section: Resultssupporting

confidence: 82%

“…Slight differences in the lengths of the M−O bonds in compounds 3, 4, and 5 result from the different lengths of the ionic radii of the lanthanide cations. These values correspond to the length of the M−O bonds found in the compounds Eu, Dy, and Er described by Huang et al 44 and Tb, Dy, Ho, and Er reported by Li et al, 45 lanthanide compounds described by Li et al, 45 in which three chlorine anions coordinate to the metal cation. Intramolecular hydrogen bonds additionally stabilize the structures of 3−5 coordination entities.…”

Section: ■ Introductionsupporting

confidence: 76%

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Synthesis, Crystal Structures, and Optical and Magnetic Properties of Samarium, Terbium, and Erbium Coordination Entities Containing Mono-Substituted Imine Silsesquioxane Ligands

et al. 2023

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Mono-substituted cage-like silsesquioxanes of the T8-type can play the role of potential ligands in the coordination chemistry. In this paper, we report on imine derivatives as ligands for samarium, terbium, and erbium cations and discuss their efficient synthesis, crystal structures, and magnetic and optical properties. X-ray analysis of the lanthanide coordination entities [MCl3(POSS)3]·2THF [M = Er3+ (3), Tb3+ (4), Sm3+ (5)] showed that all three compounds crystallize in the same space group with similar lattice parameters. All compounds contain an octahedrally coordinated metal atom, and additionally, 3 and 5 structures are strictly isomorphous. However, surprisingly, there are two different molecules in the crystal structure of the terbium coordination entity 4, monomer (sof 65%) and dimer (sof 35%), with one and two metal centers. Absorption measurements of the investigated materials recorded at 300 K showed that regardless of the lanthanide involved, their energy band gap equals 2.7 eV. Moreover, the analogues containing Tb3+ and Sm3+ exhibit luminescence typical of these rare earth ions in the visible and infrared spectral range, while the compound with Er3+ does not generate any emission. Direct current variable-temperature magnetic susceptibility measurements on polycrystalline samples of 3–5 were performed between 1.8 and 300 K. The magnetic properties of 3 and 4 are dominated by the crystal field effect on the Er3+ and Tb3+ ions, respectively, hiding the magnetic influence between the magnetic cations of adjacent molecules. Complex 5 exhibits a nature typical for the paramagnetism of the samarium(III) cation.

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Section: Resultssupporting

confidence: 82%

Section: ■ Introductionsupporting

confidence: 76%

Synthesis, Crystal Structures, and Optical and Magnetic Properties of Samarium, Terbium, and Erbium Coordination Entities Containing Mono-Substituted Imine Silsesquioxane Ligands

et al. 2023

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“…Cages composed of ligands bearing dynamic covalent bonds, which form in situ by subcomponent self-assembly, have grown in interest over the last decade. [66][67][68][69][70][71][72][73] These systems enable cage-to-cage transformations to occur via exchange of aldehyde or amine subcomponents, rather than complete ligands. Such processes are driven by the formation of more thermodynamically stable complexes when new subcomponents are introduced, driven by the difference in electronic and steric properties of various subcomponents, or the chelate effect.…”

Section: Transformations Induced Through Subcomponent Exchangementioning

confidence: 99%

Transformation networks of metal–organic cages controlled by chemical stimuli

et al. 2022

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Section: Polynuclear Lanthanide Complexes: Discrete Oligomersmentioning

confidence: 99%

Circularly polarized luminescence of lanthanide complexes: From isolated individuals, discrete oligomers, to hierarchical assemblies

Zhang

Dong

et al. 2022

InfoMat

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Circularly polarized luminescence (CPL) is the emission featured spatial orientation equivalent to circular dichroism. Owning to the unique magnetic dipole-allowed but electric-dipole-forbidden 4f ! 4f transitions, chiral lanthanide complexes have been recognized as ideal candidates to achieve unprecedented luminescence dissymmetry factor (g lum ). Their inherent electric-dipole-forbidden transition can be partly allowed, through the rational design of coordination ligands to lower the surrounding symmetry, further endowing them with relatively high quantum yields (QYs). Moreover, the blossom of supramolecular chemistry in lanthanide complexes allows for the construction of discrete oligomers and hierarchical assemblies, rendering them with enhanced chiroptical activities. Here, we deploy this review by summarizing recent advances in the chiroptical properties of lanthanide complexes, spanning multiple scales from isolated mononuclear individuals, discrete polynuclear oligomers, to infinite hierarchical assemblies. We first introduce the basic concept and several important parameters for the assessment of CPL activity. Then, isolated mononuclear lanthanide complexes coordinated with different types of antennas, along with the unique chirality transfer and induction in achiral lanthanide complexes were discussed. Next, the systematical discussion on chiroptical properties in discrete polynuclear lanthanide oligomers and infinite hierarchical lanthanide assemblies was presented. Meanwhile, the state-of-the-art applications of CPL-active lanthanide complexes were revisited. We end up this review with the conclusion and prospects, involving the rational design of ligands, directed and hierarchically precise self-assembly, and extending applications of chiral lanthanide complexes.

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Self-assembly and luminescence of trinuclear lanthanide based supramolecular circular helicates

Abstract: A series of trinuclear lanthanide circular helicates [Ln3L3]Cl3 have been synthesized via supramolecular subcomponent self-assembly. Photophysical studies demonstrate that the unique helical bis-tetradentate 1,29-dialdehyde ligand L2- could serve as an...

Cited by 7 publications

References 24 publications

Synthesis, Crystal Structures, and Optical and Magnetic Properties of Samarium, Terbium, and Erbium Coordination Entities Containing Mono-Substituted Imine Silsesquioxane Ligands

Synthesis, Crystal Structures, and Optical and Magnetic Properties of Samarium, Terbium, and Erbium Coordination Entities Containing Mono-Substituted Imine Silsesquioxane Ligands

Transformation networks of metal–organic cages controlled by chemical stimuli

Circularly polarized luminescence of lanthanide complexes: From isolated individuals, discrete oligomers, to hierarchical assemblies

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