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.

中文翻译：

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氨基酸衍生物诱导的两对手性镧系元素-氧簇Ln14

两对高核手性镧系元素-氧代簇的纯对映体，分子式为 [Y ₁₄ (L) ₁₆ ( μ ₃ -OH) ₁₆ (H ₂ O) ₂₀ ]·(ClO ₄ ) ₁₀ · x H ₂ O ( x ≈ 55；L = L -L ⁻对于L -Y ₁₄；L = D -L ⁻对于D -Y ₁₄ ) 和 [Dy ₁₄ (L) ₁₆ ( μ ₃ -OH) ₁₆ (H₂ O) ₂₀ ]·(ClO ₄ ) ₁₀ · x H ₂ O（ x ≈ 67；L = L -L ^-对于L -Dy ₁₄ ; L = D -L ^-对于D -Dy ₁₄）手性配体N-乙酰基-L-丙氨酸 ( L- HL) 和N-乙酰基-D-丙氨酸 ( D- HL)。结构分析表明，四个类立方烷单元作为共享顶点的积木形成了镧系元素-氧簇单元{(ClO₄ ) ₂ @[Y ₁₂ ( μ ₃ -OH) ₁₆ ]} ¹⁸⁺以两个 ClO ₄ ^-作为阴离子模板。剩余的Y ³⁺离子分别通过四个L -L ^-连接到{(ClO ₄ ) ₂ @[Y ₁₂ ( μ ₃ -OH) ₁₆ ]} ¹⁸⁺的相反位置。高分辨率电喷雾电离质谱 (HRESI-MS) 捕获了簇碎片 {Y ₁₂ (OH) _{16− x} (O) _{x 的信号}} ( x = 4, 5, 6, 7, 8) 和 {Y ₁₂ ( L -L) ₁₂ (OH) _{16− x} (O) _x } ₂ ( x = 4, 5, 12)的完整二聚体来自L -Y ₁₄在甲醇和二氯甲烷的混合溶液中，表明 {Ln ₁₂ (OH) _{16- x} (O) _x } 是一个稳定的簇单元，可以在溶液中进一步组装成更高核的镧系元素-氧簇。化合物L -Y ₁₄ / D -Y ₁₄的固态圆二色(CD)光谱和L -Dy ₁₄ / D -Dy ₁₄在 220-250 nm 范围内显示出镜面对称效应。磁性研究表明，L -Dy ₁₄具有弱的反铁磁相互作用，并且在没有直流场的情况下表现出类似 SMM 的行为。