Cluster-Geometry-Associated Metal-Metal Bonding in Trimetallic Carbide Clusterfullerenes
Cluster-Geometry-Associated Metal-Metal Bonding in Trimetallic Carbide Clusterfullerenes
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DOI：
10.1021/acs.inorgchem.2c01399
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发表时间：
2022-07-15
影响因子：
4.6
通讯作者：
Lu，Xing
中科院分区：
文献类型：
--
作者：
Hu，Shuaifeng;Zhao，Pei;Lu，Xing
金属团簇的几何构型对成键性质有重要影响。在此，我们报道了前所未有的铒基三金属簇合物富勒烯，即Er3C2@Ih（7）-C80的晶体学表征，其中内部Er 3C 2簇合物呈现出提升的蝙蝠射线构型，C2单元在Er 3平面上方升高了1.62 π。在该平面内，Er 1···Er 2、Er 1···Er 2A和Er 2···Er 2A的Er··Er距离分别为3.4051（15）、3.4051（15）和3.3178（15）nm，落入金属-金属键合的范围。密度泛函理论计算揭示了Er_3C_2@Ih（7）-C_80中的Er-Er-Er键为三中心单电子键，其中一个电子为三种金属共用，其特殊的电子结构可表示为（Er_3）_8+（C_2）_2-@C_80_6-。有趣的是，通过对M3C2@C2n（M = Sc，Y，Lu）系列包封团簇的几何构型的进一步观察，我们发现团簇内部的蝙蝠射线提升构型与内部金属间成键相互作用的形成明显相关.这一发现提供了对金属-金属键合性质的深入了解，并为单分子磁体的设计提供了指导。
Geometry configurations of the metallic clusters play a significant role in the involved bonding nature. Herein, we report the crystallographic characterization of unprecedented erbium-based trimetallic clusterfullerenes, namely, Er3C2@Ih(7)-C80, in which the inner Er3C2cluster presents a lifted bat ray configuration with the C2unit elevated by ∼1.62 Å above the Er3plane. Within the plane, the Er···Er distances for Er1···Er2, Er1···Er2A, and Er2···Er2A are 3.4051(15), 3.4051(15), and 3.3178(15) Å, respectively, falling into the range of the metal–metal bonding. Density functional theory calculations unveil the three-center-one-electron Er–Er–Er bond in Er3C2@Ih(7)-C80with one electron shared by three metals, and thus, its exceptional electronic structure can be expressed as (Er3)8+(C2)2–@C806–. Interestingly, with the further observation on the geometry configurations of the encapsulated clusters in M3C2@C2n(M = Sc, Y, and Lu) series, we find that the lifted bat ray configuration of the inner cluster is explicitly associated with the formation of the bonding interactions between the inner metals. This finding provides insights into the nature of metal–metal bonding and gives guidelines for the design of the single-molecule magnet.