Liu Chao, Tkachenko Nikolay V, Popov Ivan A, Fedik Nikita, Min Xue, Xu Cong-Qiao, Li Jun, McGrady John E, Boldyrev Alexander I, Sun Zhong-Ming
School of Materials Science and Engineering, State Key Laboratory of Elemento-Organic Chemistry, Tianjin Key Lab for Rare Earth Materials and Applications, Centre for Rare earth and inorganic functional materials, Nankai University, Tianjin, 300350, China.
College of Chemistry and Chemical Engineering, Central South University, Changsha, 410083, Hunan, P. R. China.
Angew Chem Int Ed Engl. 2019 Jun 17;58(25):8367-8371. doi: 10.1002/anie.201904109. Epub 2019 May 13.
We report the characterization of the compound [K([2.2.2]crypt)] [In Sb ], which proves to contain a 1:1 mixture of [Sb@In Sb ] and [Sb@In Sb ] . The tri-anion displays perfect T symmetry, the first completely inorganic molecule to do so, and contains eight equivalent In centers in a cube. The gas-phase potential energy surface of the penta-anion has eight equivalent minima where the extra pair of electrons is localized on one In center, and these minima are linked by low-lying transition states where the electron pair is delocalized over two adjacent centers. The best fit to the electron density is obtained from a model where the structure of the 5- cluster lies close to the gas-phase transition state.
我们报道了化合物[K([2.2.2]穴醚)] [In Sb ]的表征，结果表明其包含[Sb@In Sb ]和[Sb@In Sb ]的1:1混合物。该三阴离子呈现出完美的T对称性，是首个具有此性质的完全无机分子，且在一个立方体中包含八个等效的In中心。五阴离子的气相势能面有八个等效的极小值，其中额外的一对电子定域在一个In中心上，这些极小值通过低能过渡态相连，在过渡态中电子对在两个相邻中心上离域。对电子密度的最佳拟合是通过一个模型得到的，该模型中5-簇的结构接近气相过渡态。
