Titanium/yttrium mixed metal nitride clusterfullerene TiY2N@C80: synthesis, isolation, and effect of the group-III metal

Titanium/yttrium mixed metal nitride clusterfullerene (MMNCF) TiY(2)N@C(80) has been successfully synthesized, representing the first Ti-containing non-scandium MMNCF. TiY(2)N@C(80) has been isolated by multistep HPLC and characterized by various spectroscopies in combination with DFT computations. The electronic absorption property of TiY(2)N@C(80) was characterized by UV-vis-NIR spectroscopy, indicating the resemblance to that of TiSc(2)N@C(80) with broad shoulder absorptions. The optical band gap of TiY(2)N@C(80) (1.39 eV) is very close to that of TiSc(2)N@C(80) (1.43 eV) but much smaller than that of Y(3)N@C(80)(I(h), 1.58 eV). Such a resemblance of the overall absorption feature of TiY(2)N@C(80) to TiSc(2)N@C(80) suggests that TiY(2)N@C(80) has a similar electronic configuration to that of TiSc(2)N@C(80), that is, (TiY(2)N)(6+)@C(80)(6-). FTIR spectroscopic study and DFT calculations accomplish the assignment of the C(80):I(h) isomer to the cage structure of TiY(2)N@C(80), with the C(1) conformer being the lowest energy structure, which is different from the C(s) conformer assigned to TiSc(2)N@C(80). The electrochemical properties of TiY(2)N@C(80) were investigated by cyclic voltammetry, revealing the reversible first oxidation and first reduction step with E(1/2) at 0.00 and -1.13 V, respectively, both of which are more negative than those of TiSc(2)N@C(80), while the electrochemical energy gap of TiY(2)N@C(80) (1.11 V) is almost the same as that of TiSc(2)N@C(80) (1.10 V). Contrary to the reversible first reduction step, the second and third reduction steps of TiY(2)N@C(80) are irreversible, and this redox behavior is dramatically different from that of TiSc(2)N@C(80), which shows three reversible reduction steps, indicating the strong influence of the encaged group-III metal (Y or Sc) on the electronic properties of TiM(2)N@C(80) (M = Y, Sc).