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Investigation into the molecular structure and energetic stability of endohedral and exohedral metallofullerene derivatives of C 24
Author(s) -
Haynes Caleb A.,
Lopez Serafin,
Beran Kyle A.
Publication year - 2019
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25992
Subject(s) - metallofullerene , endohedral fullerene , bond length , chemistry , homo/lumo , carbon fibers , crystallography , spin states , metal , ion , density functional theory , molecular geometry , spin (aerodynamics) , fullerene , computational chemistry , materials science , molecule , inorganic chemistry , thermodynamics , physics , crystal structure , organic chemistry , composite number , composite material
Density‐functional theory was applied to the investigation of the structural and electronic properties of C 24 fullerene derivatives. Transition metals (TMs) from groups 11 and 12, in various oxidation and spin‐states, are inserted at either endohedral (TM@C 24 ) or exohedral (TM‐C 24 ) sites and their subsequent energetic stabilities are assessed. With the exception of Ag@C 24 , all derivatives are predicted to occupy a minimum on the potential energy surface. The optimized exohedral TM‐C 24 geometries yield TM‐C bond lengths that are consistent with comparable carbon‐metal bond lengths, and the overwhelming majority of the derivatives result in a slight deformation of the C 24 cage as the bonding carbon takes on more sp 3 character. All of the TM@C 24 equilibrium structures maintain the integrity of the cage structure with a moderate increase in the diameter. All neutral exohedral and endohedral complexes favor the low spin‐state; conversely, all of the charged exohedral complexes prefer the high spin‐state, with the exception of Cu‐C 24 1+ molecular ion. The Group 12 charged endohedral derivatives prefer the low spin‐state, whereas the Group 11 molecular ions do not necessarily exhibit a definitive trend. Analysis of the energetic data predicts that of the lowest energy endohedral molecular species only four are predicted to be energetically favorable in terms of insertion energy and an advantageous HOMO‐LUMO gap: Cu@C 24 2+ , Ag@C 24 1+ , Au@C 24 3+ , and Zn@C 24 2+ .