A combination of experimental (SQUID magnetometry) and quantum‐chemical (BS‐DFT, CASSCF(n,m)/NEVPT2, DDCI3) methods is used to probe the influence of terminal ligands on magnetic exchange coupling in the series of [Cu₂(μ₂‐OAc)₄L₂] complexes with O‐donor terminal ligands extended by two novel complexes containing phosphine oxide ligands. The possibilities and limitations of these approaches are discussed. The influence of terminal ligands on magnetic superexchange interaction was quantified by two contributions—the first contribution is associated with structural changes within the {Cu(μ₂‐OAc)₄Cu} core, while the second contribution is due to the difference in the electronic influence of different terminal ligands at a given core geometry. Both contributions were found to be approximately of the same order of magnitude. These results indicate that magnetic exchange coupling, known to be highly sensitive to the distortions in core geometry, is not solely determined by the core structure. Our findings are consistent with the fact that various one‐ and multiparameter magnetostructural correlations reported in the literature have only a qualitative predictive capability.

中文翻译：

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洞察末端配体对一系列二聚乙酸铜（II）加合物中磁交换耦合的影响

实验方法（SQUID磁力法）和量子化学方法（BS-DFT，CASSCF（n，m）/ NEVPT2，DDCI3）结合使用，以探讨末端配体对[Cu ₂（μ ₂ -OAc）₄大号₂ ]用O-供体配体终端通过含有氧化膦配体的两个新的配合物延伸物。讨论了这些方法的可能性和局限性。上磁性超交换相互作用终端的配体的影响是由两个定量贡献-第一贡献与{CU内的结构变化相关联（μ ₂ -OAc）₄Cu}核，而第二个贡献是由于在给定的核几何结构下，不同末端配体的电子影响力不同。发现这两种贡献近似相同的数量级。这些结果表明，已知对磁芯几何形状的变形高度敏感的磁交换耦合并不完全由磁芯结构决定。我们的发现与以下事实相吻合：文献中报道的各种单参数和多参数磁结构相关性仅具有定性预测能力。