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Electronic Structure and Redox Properties of Metal Nitride Endohedral Fullerenes M 3 N@C 2 n (M=Sc, Y, La, and Gd; 2 n =80, 84, 88, 92, 96)
Author(s) -
Valencia Ramón,
RodríguezFortea Antonio,
Clotet Anna,
de Graaf Coen,
Chaur Manuel N.,
Echegoyen Luis,
Poblet Josep M.
Publication year - 2009
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.200900728
Subject(s) - redox , endohedral fullerene , electrochemistry , metal , fullerene , nitride , electronic structure , materials science , crystallography , chemistry , computational chemistry , inorganic chemistry , nanotechnology , electrode , metallurgy , organic chemistry , layer (electronics)
An extensive study of the redox properties of metal nitride endohedral fullerenes (MNEFs) based on DFT computational calculations has been performed. The electronic structure of the singly oxidized and reduced MNEFs has been thoroughly analyzed and the first anodic and cathodic potentials, as well as the electrochemical gaps, have been predicted for a large number of M 3 N@C 2 n systems (M=Sc, Y, La, and Gd; 2 n =80, 84, 88, 92, and 96). In particular, calculations that include thermal and entropic effects correctly predict the different anodic behavior of the two isomers ( I h and D 5h ) of Sc 3 N@C 80 , which is the basis for their electrochemical separation. Important differences were found in the electronic structure of reduced M 3 N@C 80 when M=Sc or when M is a more electropositive metal, such as Y or Gd. Moreover, the changes in the electrochemical gaps within the Gd 3 N@C 2 n series (2 n =80, 84, and 88) have been rationalized and the use of Y‐based computational models to study the Gd‐based systems has been justified. The redox properties of the largest MNEFs characterized so far, La 3 N@C 2 n (2 n =92 and 96), were also correctly predicted. Finally, the quality of these predictions and their usefulness in distinguishing the carbon cages for MNEFs with unknown structures is discussed.