Yan Yingjing, Abella Laura, Sun Rong, Fang Yu-Hui, Roselló Yannick, Shen Yi, Jin Meihe, Rodríguez-Fortea Antonio, de Graaf Coen, Meng Qingyu, Yao Yang-Rong, Echegoyen Luis, Wang Bing-Wu, Gao Song, Poblet Josep M, Chen Ning
College of Chemistry, Chemical Engineering and Materials Science, and State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou, Jiangsu, 215123, P. R. China.
Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel·lí Domingo 1, 43007, Tarragona, Spain.
Nat Commun. 2023 Oct 20;14(1):6637. doi: 10.1038/s41467-023-42165-x.
Understanding metal-metal bonding involving f-block elements has been a challenging goal in chemistry. Here we report a series of mixed-valence di-metallofullerenes, ThDy@C (2n = 72, 76, 78, and 80) and ThY@C (2n = 72 and 78), which feature single electron actinide-lanthanide metal-metal bonds, characterized by structural, spectroscopic and computational methods. Crystallographic characterization unambiguously confirmed that Th and Y or Dy are encapsulated inside variably sized fullerene carbon cages. The ESR study of ThY@D(5)-C shows a doublet as expected for an unpaired electron interacting with Y, and a SQUID magnetometric study of ThDy@D(5)-C reveals a high-spin ground state for the whole molecule. Theoretical studies further confirm the presence of a single-electron bonding interaction between Y or Dy and Th, due to a significant overlap between hybrid spd orbitals of the two metals.
理解涉及f族元素的金属-金属键一直是化学领域一个具有挑战性的目标。在此，我们报道了一系列混合价态的双金属富勒烯，ThDy@C（2n = 72、76、78和80）以及ThY@C（2n = 72和78），它们具有单电子锕系-镧系金属-金属键，通过结构、光谱和计算方法对其进行了表征。晶体学表征明确证实Th和Y或Dy被封装在尺寸各异的富勒烯碳笼内部。对ThY@D(5)-C的电子顺磁共振研究显示出一个双重峰，这与一个未成对电子与Y相互作用的预期相符，而对ThDy@D(5)-C的超导量子干涉仪磁测量研究揭示了整个分子的高自旋基态。理论研究进一步证实了Y或Dy与Th之间存在单电子键相互作用，这是由于两种金属的杂化spd轨道之间存在显著重叠。
