<br>亲电 CF3 添加稳定的 Nd2@C80 的 Ih 和 D5h 笼异构体中的 Nd─Nd 键,Advanced Science

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亲电 CF3 添加稳定的 Nd2@C80 的 Ih 和 D5h 笼异构体中的 Nd─Nd 键
Advanced Science ( IF 14.3 ) Pub Date : 2023-11-09 , DOI: 10.1002/advs.202305190
Wei Yang ₁ , Georgios Velkos ₁ , Marco Rosenkranz ₁ , Sandra Schiemenz ₁ , Fupin Liu ₁ , Alexey A Popov ₁

Affiliation

4f 元素之间具有金属-金属键的分子化合物的合成被认为是镧系金属化学中令人着迷的里程碑之一。由于对其磁性的兴趣，此类研究的主要焦点集中在重稀土元素上，而轻稀土元素之间的键合仍未得到探索。在这项工作中，Nd-二金属富勒烯中的 Nd─Nd 键合作为早期镧系元素之间金属-金属键合的案例研究得到了证明。结合实验和计算研究证明原始Nd ₂ @C ₈₀具有开壳结构，单个电子占据Nd─Nd键合轨道。 Nd ₂ @C ₈₀通过单电子还原以及进一步通过亲电CF ₃加成至[Nd ₂ @C ₈₀ ] ^-来稳定。单晶X射线衍射揭示了两种具有D _5h -C ₈₀和I _h -C ₈₀碳笼的Nd ₂ @C ₈₀ (CF ₃ )异构体的形成，两者均具有单电子Nd─Nd键，长度为3.78–3.79 埃。分析了外嵌CF ₃基团和内嵌金属二聚体在确定加合物分子结构中的相互影响。与 Tb 或 Dy 类似物（具有高磁化截止温度的强单分子磁体）不同，Nd ₂ @I _h -C ₈₀ (CF ₃ ) 中的磁化缓慢弛豫仅可通过异相磁化率检测到3 K 且存在磁场的情况下。

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Nd─Nd Bond in Ih and D5h Cage Isomers of Nd2@C80 Stabilized by Electrophilic CF3 Addition

Synthesis of molecular compounds with metal–metal bonds between 4f elements is recognized as one of the fascinating milestones in lanthanide metallochemistry. The main focus of such studies is on heavy lanthanides due to the interest in their magnetism, while bonding between light lanthanides remains unexplored. In this work, the Nd─Nd bonding in Nd-dimetallofullerenes as a case study of metal–metal bonding between early lanthanides is demonstrated. Combined experimental and computational study proves that pristine Nd₂@C₈₀ has an open shell structure with a single electron occupying the Nd─Nd bonding orbital. Nd₂@C₈₀ is stabilized by a one-electron reduction and further by the electrophilic CF₃ addition to [Nd₂@C₈₀]⁻. Single-crystal X-ray diffraction reveals the formation of two Nd₂@C₈₀(CF₃) isomers with D_5h-C₈₀ and I_h-C₈₀ carbon cages, both featuring a single-electron Nd─Nd bond with the length of 3.78–3.79 Å. The mutual influence of the exohedral CF₃ group and endohedral metal dimer in determining the molecular structure of the adducts is analyzed. Unlike Tb or Dy analogs, which are strong single-molecule magnets with high blocking temperature of magnetization, the slow relaxation of magnetization in Nd₂@I_h-C₈₀(CF₃) is detectable via out-of-phase magnetic susceptibility only below 3 K and in the presence of magnetic field.

更新日期：2023-11-09

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