Hu Shuaifeng, Shen Wangqiang, Yang Le, Duan Guangxiong, Jin Peng, Xie Yunpeng, Akasaka Takeshi, Lu Xing
State Key Laboratory of Materials Processing and Die &, Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, 1037 Luoyu Road, Wuhan, 430074, P. R. China.
School of Materials Science and Engineering, Hebei University of Technology, Tianjin, 300130, P. R. China.
Chemistry. 2019 Sep 2;25(49):11538-11544. doi: 10.1002/chem.201902321. Epub 2019 Aug 8.
Successful isolation and characterization of a series of Er-based dimetallofullerenes present valuable insights into the realm of metal-metal bonding. These species are crystallographically identified as Er @C (6)-C , Er @C (8)-C , Er @C (12)-C , and Er @C (9)-C , in which the structure of the C (12)-C cage is unambiguously characterized for the first time by single-crystal X-ray diffraction. Interestingly, natural bond orbital analysis demonstrates that the two Er atoms in Er @C (6)-C , Er @C (8)-C , and Er @C (9)-C form a two-electron-two-center Er-Er bond. However, for Er @C (12)-C , with the longest Er⋅⋅⋅Er distance, a one-electron-two-center Er-Er bond may exist. Thus, the difference in the Er⋅⋅⋅Er separation indicates distinct metal bonding natures, suggesting a distance-dependent bonding behavior for the internal dimetallic cluster. Additionally, electrochemical studies suggest that Er @C are good electron donors instead of electron acceptors. Hence, this finding initiates a connection between metal-metal bonding chemistry and fullerene chemistry.
一系列基于铒的双金属富勒烯的成功分离和表征为金属-金属键合领域提供了宝贵的见解。这些物种通过晶体学鉴定为Er@C(6)-C、Er@C(8)-C、Er@C(12)-C和Er@C(9)-C，其中C(12)-C笼的结构首次通过单晶X射线衍射得到明确表征。有趣的是，自然键轨道分析表明，Er@C(6)-C、Er@C(8)-C和Er@C(9)-C中的两个铒原子形成了一个双电子双中心的Er-Er键。然而，对于具有最长Er⋅⋅⋅Er距离的Er@C(12)-C，可能存在一个单电子双中心的Er-Er键。因此，Er⋅⋅⋅Er间距的差异表明了不同的金属键合性质，这表明内部双金属簇的键合行为与距离有关。此外，电化学研究表明，Er@C是良好的电子供体而非电子受体。因此，这一发现开启了金属-金属键合化学与富勒烯化学之间的联系。
