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Quantum Chemical Insight of the Dimetallic Sulfide Endohedral Fullerene Sc 2 S@C 70 : Does It Possess the Conventional D 5 h Cage?
Author(s) -
Yang Tao,
Zhao Xiang,
Nagase Shigeru
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201203388
Subject(s) - fullerene , endohedral fullerene , chemistry , crystallography , atomic orbital , sulfide , computational chemistry , supramolecular chemistry , chemical shift , electron , physics , crystal structure , organic chemistry , quantum mechanics
Like C 60 , C 70 is one of the most representative fullerenes in fullerene science. Even though there are 8149 C 70 isomers, only two of them have been found before: the conventional D 5 h and an isolated pentagon rule (IPR)‐violating C 2 v (7854). Through the use of quantum chemical methods, we report a new unconventional C 70 isomer, C 2 (7892), which survives in the form of dimetallic sulfide endohedral fullerene Sc 2 S@C 70 . Compared with the IPR‐obeying C 70 and the C 2 v (7854) fullerene with three pairs of pentagon adjacencies, the C 2 (7892) cage violates the isolated pentagon rule and has two pairs of pentagon adjacencies. In Sc 2 S@ C 2 (7892)‐C 70 , two scandium atoms coordinate with two pentalene motifs, respectively, presenting two equivalent ScS bonds. The strong coordination interaction, along with the electron transfer from the Sc 2 S cluster to the fullerene cage, results in the stabilization of the non‐IPR endohedral fullerene. The electronic structure of Sc 2 S@C 70 can be formally described as [Sc 2 S] 4+ @[C 70 ] 4− ; however, a substantial overlap between the metallic orbitals and cage orbitals has also been found. Electrochemical properties and electronic absorption, infrared, and 13 C NMR spectra of Sc 2 S@C 70 have been calculated theoretically.