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Quantum Chemical Insight of the Dimetallic Sulfide Endohedral Fullerene Sc2S@C70: Does It Possess the Conventional D5h Cage?

Authors

  • Tao Yang,

    1. Institute for Chemical Physics & Department of Chemistry, State Key Laboratory of Electrical Insulation and Power Equipment, Xi'an Jiaotong University, Xi'an 710049 (P.R. China), Fax: (+86) 29-8266-8559
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  • Prof. Dr. Xiang Zhao,

    Corresponding author
    1. Institute for Chemical Physics & Department of Chemistry, State Key Laboratory of Electrical Insulation and Power Equipment, Xi'an Jiaotong University, Xi'an 710049 (P.R. China), Fax: (+86) 29-8266-8559
    • Institute for Chemical Physics & Department of Chemistry, State Key Laboratory of Electrical Insulation and Power Equipment, Xi'an Jiaotong University, Xi'an 710049 (P.R. China), Fax: (+86) 29-8266-8559
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  • Prof. Dr. Shigeru Nagase

    1. Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103 (Japan)
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Abstract

Like C60, C70 is one of the most representative fullerenes in fullerene science. Even though there are 8149 C70 isomers, only two of them have been found before: the conventional D5h and an isolated pentagon rule (IPR)-violating C2v(7854). Through the use of quantum chemical methods, we report a new unconventional C70 isomer, C2(7892), which survives in the form of dimetallic sulfide endohedral fullerene Sc2S@C70. Compared with the IPR-obeying C70 and the C2v(7854) fullerene with three pairs of pentagon adjacencies, the C2(7892) cage violates the isolated pentagon rule and has two pairs of pentagon adjacencies. In Sc2S@C2(7892)-C70, two scandium atoms coordinate with two pentalene motifs, respectively, presenting two equivalent Sc[BOND]S bonds. The strong coordination interaction, along with the electron transfer from the Sc2S cluster to the fullerene cage, results in the stabilization of the non-IPR endohedral fullerene. The electronic structure of Sc2S@C70 can be formally described as [Sc2S]4+@[C70]4−; however, a substantial overlap between the metallic orbitals and cage orbitals has also been found. Electrochemical properties and electronic absorption, infrared, and 13C NMR spectra of Sc2S@C70 have been calculated theoretically.

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