Issue 39, 2021

Two pairs of chiral lanthanide–oxo clusters Ln14 induced by amino acid derivatives

Abstract

Two pairs of pure enantiomers of high-nuclearity chiral lanthanide–oxo clusters with the formulas [Y14(L)16(μ3-OH)16(H2O)20]·(ClO4)10·xH2O (x ≈ 55; L = L-L for L-Y14; L = D-L for D-Y14) and [Dy14(L)16(μ3-OH)16(H2O)20]·(ClO4)10·xH2O (x ≈ 67; L = L-L for L-Dy14; L = D-L for D-Dy14) were prepared in the presence of chiral ligands N-acetyl-L-alanine (L-HL) and N-acetyl-D-alanine (D-HL). Structural analysis showed that four cubane-like units as building blocks sharing vertices formed the lanthanide–oxo cluster unit {(ClO4)2@[Y12(μ3-OH)16]}18+ with two ClO4 as anion templates. The remaining Y3+ ions were connected to the opposite position of {(ClO4)2@[Y12(μ3-OH)16]}18+ through four L-L, respectively. High-resolution electrospray ionization mass spectrometry (HRESI-MS) captured the signals of the cluster fragment {Y12(OH)16−x(O)x} (x = 4, 5, 6, 7, 8) and the unbroken dimer of {Y12(L-L)12(OH)16−x(O)x}2 (x = 4, 5, 12) from L-Y14 in a mixed solution of methanol and dichloromethane, suggesting that {Ln12(OH)16−x(O)x} is a stable cluster unit that could be further assembled into higher-nuclearity lanthanide–oxo clusters in solution. The solid-state circular dichroism (CD) spectra of compounds L-Y14/D-Y14 and L-Dy14/D-Dy14 displayed mirror symmetry effects in the range of 220–250 nm. The study of magnetic properties showed that L-Dy14 had a weak antiferromagnetic interaction and displayed SMM-like behavior in the absence of a dc field.

Graphical abstract: Two pairs of chiral lanthanide–oxo clusters Ln14 induced by amino acid derivatives

Supplementary files

Article information

Article type
Paper
Submitted
21 juil. 2021
Accepted
22 août 2021
First published
24 août 2021

CrystEngComm, 2021,23, 6923-6929

Two pairs of chiral lanthanide–oxo clusters Ln14 induced by amino acid derivatives

T. Lu, J. Yin, C. Chen, H. Shi, J. Zheng, Z. Liu, X. Fang and X. Zheng, CrystEngComm, 2021, 23, 6923 DOI: 10.1039/D1CE00948F

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