Metathesis of the isomorphous 15‐metallacrown‐5 complexes {[LnCu₅(GlyHA)₅(SO₄)(H₂O)_6.5]}₂(SO₄)·6H₂O (Ln^III = Pr, Nd, Sm, Eu; GlyHA^2– = glycinehydroxamate) with excess p‐bdc^2– (p‐bdc^2– = terephthalate) gave pairs of isomorphous complexes {[LnCu₅(GlyHA)₅(CO₃)(H₂O)₄]₂(p‐bdc)}·15H₂O [Ln = Pr (1) and Nd (2)] and {[LnCu₅(GlyHA)₅(SO₄)(H₂O)_x]₂(p‐bdc)}·yH₂O [Sm (3) x = 5, y = 12; Eu (4), x = 4, y = 14] as outcomes of partial sulfate replacement. Complexes 1–4 are discrete dimers with two 15‐metallacrown‐5 blocks {LnCu₅}³⁺, a bridging p‐bdc^2– and a bidentate capping anion on each Ln³⁺. The anion caps in 1 and 2 are carbonates from atmospheric CO₂ capture, while in 3 and 4 the anion caps are sulfates. Between 3 K and 300 K, intrametallacycle antiferromagnetic exchange interactions amongst the Cu²⁺ dominate the magnetic properties of 1–4, while for the Ln³⁺, spin‐orbit coupling and crystal field effects are significant, the former being greater for Sm³⁺ and Eu³⁺. The experimental χ_MT vs. T data were fitted with an additive model reflecting the dominance of the Cu···Cu superexchange, while Ln³⁺···Cu²⁺ exchange interactions were taken into account through a molecular field approach. The best‐fit values (–2J_Cu–Cu) for the intercopper superexchange interactions range from 88 to 120 cm^–1; the g‐factors, spin‐orbit coupling (λ) and axial crystal field splitting (Δ) parameter values are typical for Ln^III.

中文翻译：

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具有对苯二甲酸酯的LnIII–CuII 15–Metallacrown-5二聚体的磁性（LnIII = Pr，Nd，Sm，Eu）

同构的15-金属镧5络合物的复分解{[LnCu ₅（GlyHA）₅（SO ₄）（H ₂ O）_6.5 ]} ₂（SO ₄）· 6H ₂ O（Ln ^III = Pr，Nd，Sm，Eu ; GlyHA ^2- = glycinehydroxamate）与过量的p -bdc ^2-（p -bdc ^2- =对苯二甲酸乙二酯），得到同晶复合物的双{[LnCu ₅（GlyHA）₅（CO ₃）（H ₂ O）₄ ] ₂（p ‐bdc）}· 15H ₂ O [Ln = Pr（1）和Nd（2）]和{[LnCu ₅（GlyHA）₅（SO ₄）（H ₂ O）_x ] ₂（p -bdc）} · y H ₂ O [ Sm（3）x = 5，y = 12；Eu（4），x = 4，y = 14]作为部分硫酸盐置换的结果。配合物1 - 4是具有两个15-metallacrown-5块{LnCu离散二聚体₅ } ³⁺，在每个Ln ³⁺上桥接p ‐bdc ^2–和双齿封端阴离子。1和2中的阴离子帽是从大气中捕获CO _2的碳酸盐，而3和4中的阴离子帽是硫酸盐。之间3 K和300°K，intrametallacycle铜之间的反铁磁交换相互作用²⁺的支配磁特性1 - 4，而对于LN ³⁺，自旋-轨道耦合和晶体场的影响是显著，前者是越大的Sm ^{3 +}和Eu ³⁺。实验χ_M T与T数据拟合了反映Cu ··· Cu超交换占主导地位的加性模型，而通过分子场方法考虑了Ln ³⁺ ··· Cu ²⁺交换相互作用。_铜间超交换相互作用的最佳拟合值（–2 J _Cu–Cu）范围为88至120 cm ^–1；的克-因子，自旋-轨道耦合（ λ）和轴向晶体场分裂（Δ）的参数值是典型的LN ^III。