Titanium/Yttrium Mixed Metal Nitride Clusterfullerene TiY2N@C80: Synthesis, Isolation, and Effect of the Group-III Metal

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• 作者：Chuanbao Chen ; Fupin Liu ; Shujuan Li ; Nan Wang ; Alexey A. Popov ; Mingzhi Jiao ; Tao Wei ; Qunxiang Li ; Lothar Dunsch ; Shangfeng Yang
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：March 5, 2012
• 年：2012
• 卷：51
• 期：5
• 页码：3039-3045
• 全文大小：386K
• 年卷期：v.51,no.5(March 5, 2012)
• ISSN：1520-510X

文摘

Titanium/yttrium mixed metal nitride clusterfullerene (MMNCF) TiY₂N@C₈₀ has been successfully synthesized, representing the first Ti-containing non-scandium MMNCF. TiY₂N@C₈₀ has been isolated by multistep HPLC and characterized by various spectroscopies in combination with DFT computations. The electronic absorption property of TiY₂N@C₈₀ was characterized by UV鈥搗is鈥揘IR spectroscopy, indicating the resemblance to that of TiSc₂N@C₈₀ with broad shoulder absorptions. The optical band gap of TiY₂N@C₈₀ (1.39 eV) is very close to that of TiSc₂N@C₈₀ (1.43 eV) but much smaller than that of Y₃N@C₈₀(I_h, 1.58 eV). Such a resemblance of the overall absorption feature of TiY₂N@C₈₀ to TiSc₂N@C₈₀ suggests that TiY₂N@C₈₀ has a similar electronic configuration to that of TiSc₂N@C₈₀, that is, (TiY₂N)⁶⁺@C₈₀^{6鈥?/sup>. FTIR spectroscopic study and DFT calculations accomplish the assignment of the C₈₀:I_h isomer to the cage structure of TiY₂N@C₈₀, with the C₁ conformer being the lowest energy structure, which is different from the C_s conformer assigned to TiSc₂N@C₈₀. The electrochemical properties of TiY₂N@C₈₀ were investigated by cyclic voltammetry, revealing the reversible first oxidation and first reduction step with E_1/2 at 0.00 and 鈭?.13 V, respectively, both of which are more negative than those of TiSc₂N@C₈₀, while the electrochemical energy gap of TiY₂N@C₈₀ (1.11 V) is almost the same as that of TiSc₂N@C₈₀ (1.10 V). Contrary to the reversible first reduction step, the second and third reduction steps of TiY₂N@C₈₀ are irreversible, and this redox behavior is dramatically different from that of TiSc₂N@C₈₀, which shows three reversible reduction steps, indicating the strong influence of the encaged group-III metal (Y or Sc) on the electronic properties of TiM₂N@C₈₀ (M = Y, Sc).}