A series of unique homochiral lanthanide tetranuclear quadruple-stranded helicates have been self-assembled controllably by using the intrinsic advantages of chiral bridging ligands, (S)-H L and (R)-H L, and lanthanide ions with high coordination numbers. The self-assembly process of these chiral helicates not only ensures the structural stability and quadruple-stranded feature of lanthanide cluster in the solid state and solution, but also achieves effective transfer and amplification of the chirality code from the ligand to a higher supramolecular level. Moreover, through using optical rotation, circular dichroism spectra analysis, and luminescence measurements, we demonstrate that these chiral lanthanide helicates could serve as sensitive and multi-responsive sensors to recognize and detect F anions based on the change of chiral signal and NIR luminescence simultaneously, which represents a meaningful exploration for developing functional lanthanide-based polynuclear clusters.
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http://dx.doi.org/10.1002/chem.201700827 | DOI Listing |
Chemistry
November 2024
Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, School of Chemistry and Materials Science, Heilongjiang University, 74 Xuefu Road, Harbin, 150080, China.
Hierarchical self-assembly driven by non-covalent interactions is a prevalent strategy employed by nature to construct sophisticated biomacromolecules, such as proteins. However, the construction of protein-like superstructures that rely on weaker dispersion forces-driven hierarchical assembly remains largely unexplored. Here, we report the first example of dispersion forces driving the high-order assembly of the lanthanide trinuclear circular helicate [HNEt₃]₃[Eu₃(L)₆] (ΔΔΔ-1) into a protein-like lanthanide octamer ((ΔΔΔ-1)₈-2).
View Article and Find Full Text PDFInorg Chem
December 2023
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, Jiangsu 210023, P. R. China.
Lanthanide-based molecular materials showing efficient circularly polarized luminescence (CPL) activity with a high quantum yield are attractive due to their potential applications in data storage, optical sensors, and 3D displays. Herein we present an innovative method to achieve enhanced CPL activity and a high quantum yield by doping a chromophore ligand into a coordination polymer superhelix. A series of homochiral europium(III) phosphonates with a helical morphology were prepared with the molecular formula -, -[Eu(cyampH)(nempH)]·3HO (/, = 0-5%).
View Article and Find Full Text PDFDalton Trans
October 2023
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, P. R. China.
Lanthanide peroxides show high reactivity in oxidative coupling of methane (OCM). However, the number of isolated and structurally characterized molecular species remains relatively small. To the best of our knowledge, homochiral molecule-based lanthanide peroxides have not been reported.
View Article and Find Full Text PDFChemistry
January 2023
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry Chinese Academy of Sciences, Changchun, 130022, P. R. China.
Two pairs of chiral end-on azido-bridged dinuclear hexaazamacrocycles, [Dy (L ) (N ) Cl ](BPh ) (1R/1S) and [Dy (L ) (N ) ]Cl (2R/2S) (L is hexaazamacrocyclic neutral Schiff base ligand derived from 2,6-diformylpyridine and (1R, 2R)/(1S, 2S)-diaminocyclohexane), were constructed by adjusting the molar ratio of sodium azide to Dy(III) macrocycle precursor. Structural analyses reveal that all Dy(III) centers in complexes 1R/1S and 2R/2S are nine-coordinate with hula-loop coordination geometry, and the differences between 1R/1S and 2R/2S are the terminal coordination anion and counter anion. Magnetic studies indicate that complex 2S displays typical SMM behaviors under a zero dc field, whereas 1S just shows slow relaxation of magnetization resulting from a relatively weak axial crystal field.
View Article and Find Full Text PDFJ Am Chem Soc
August 2021
Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, United States.
It is extremely difficult to anticipate the structure and the stereochemistry of a complex, particularly when the ligand is flexible and the metal node adopts diverse coordination numbers. When trivalent lanthanides (Ln) and enantiopure amino acid ligands are utilized as building blocks, self-assembly sometimes yields rare chiral polynuclear structures. In this study, an enantiopure carboxyl-functionalized amino acid-based ligand with symmetry reacts with lanthanum cations to give a homochiral porous coordination cage, (Δ/Λ)-.
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