U(2)N@I (h)(7)-C(80): fullerene cage encapsulating an unsymmetrical U(iv)[double bond, length as m-dash]N[double bond, length as m-dash]U(v) cluster.
U(2)N@I (h)(7)-C(80): fullerene cage encapsulating an unsymmetrical U(iv)[double bond, length as m-dash]N[double bond, length as m-dash]U(v) cluster.
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U2N@Ih(7)-C80：封装不对称U(IV)=N=U(V)簇的富勒烯笼
DOI：
10.1039/d0sc04677a
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发表时间：
2020-10-27
期刊：
影响因子：
8.4
通讯作者：
Chen N
中科院分区：
文献类型：
--
作者：
Li X;Roselló Y;Yao YR;Zhuang J;Zhang X;Rodríguez-Fortea A;de Graaf C;Echegoyen L;Poblet JM;Chen N
首次合成了锕系氮化簇富勒烯U2N@Ih(7)-C80，并用x射线单晶学和多光谱方法对其进行了表征。U2N@Ih(7)-C80是迄今为止第一个违反公认的氮化簇富勒烯的三金属氮化模板的内嵌富勒烯。新的UNU簇具有两个键距不均匀的UN键，分别为2.058(3)Å和1.943(3)Å，导致双核氮化物基序具有罕见的不对称结构。实验与理论相结合的研究表明，两种铀离子呈现出不同的+4和+5氧化态。量子化学研究进一步表明，f1/f2居群主要引起UNU簇的扭曲，从而导致不对称结构。对U2X@C80 （X = C， N和O）的对比研究表明，UXU簇中的U-X相互作用很难被看作是由经典的多重键形成的，而更像是一个阴离子中心离子Xq−，与两个金属离子有偏交叠，随着X的电负性的增加而减少。本研究不仅证明了富勒烯笼稳定的锕系元素团簇的独特成键变化，表现出与镧系类似物不同的成键方式，还揭示了UXU团簇（X = C， N和O）的电子结构，这对理解这些锕系元素的成键基序具有重要意义。一种新的锕系元素簇UNU被稳定在C80富勒烯笼中。U(iv)NU(v)簇具有两个键距不均匀的UN键，分别为2.058(3)Å和1.943(3)Å，形成不对称结构。
For the first time, an actinide nitride clusterfullerene, U2N@Ih(7)-C80, is synthesized and fully characterized by X-ray single crystallography and multiple spectroscopic methods. U2N@Ih(7)-C80 is by far the first endohedral fullerene that violates the well-established tri-metallic nitride template for nitride clusterfullerenes. The novel UNU cluster features two UN bonds with uneven bond distances of 2.058(3) Å and 1.943(3) Å, leading to a rare unsymmetrical structure for the dinuclear nitride motif. The combined experimental and theoretical investigations suggest that the two uranium ions show different oxidation states of +4 and +5. Quantum-chemical investigation further reveals that the f1/f2 population dominantly induces a distortion of the UNU cluster, which leads to the unsymmetrical structure. A comparative study of U2X@C80 (X = C, N and O) reveals that the U–X interaction in UXU clusters can hardly be seen as being formed by classical multiple bonds, but is more like an anionic central ion Xq− with biased overlaps with the two metal ions, which decrease as the electronegativity of X increases. This study not only demonstrates the unique bonding variety of actinide clusters stabilized by fullerene cages, showing different bonding from that observed for the lanthanide analogs, it also reveals the electronic structure of the UXU clusters (X = C, N and O), which are of fundamental significance to understanding these actinide bonding motifs. A novel actinide cluster, UNU, is stabilized inside a C80 fullerene cage. The U(iv)NU(v) cluster features two UN bonds with uneven bond distances of 2.058(3) Å and 1.943(3) Å, leading to an unsymmetrical structure.
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