title: Electronic properties and 13C NMR structural study of Y3N@C88.
abstract: In this paper, we report the synthesis, purification, (13)C NMR, and other characterization studies of Y(3)N@C(88). The (13)C NMR, UV-vis, and chromatographic data suggest an Y(3)N@C(88) having an IPR-allowed cage with D(2)(35)-C(88) symmetry. In earlier density functional theory (DFT) computational and X-ray crystallographic studies, it was reported that lanthanide (A(3)N)(6+) clusters are stabilized in D(2)(35)-C(88) symmetry cages and have reduced HOMO-LUMO gaps relative to other trimetallic nitride endohedral metallofullerene cage systems, for example, A(3)N@C(80). In this paper, we report that the nonlanthanide (Y(3)N)(6+) cluster in the D(2)(35)-C(88) cage exhibits a HOMO-LUMO gap consistent with other lanthanide A(3)N@C(88) molecules based on electrochemical measurements and DFT computational studies. These results suggest that the reduced HOMO-LUMO gap of A(3)N@C(88) systems is a property dominated by the D(2)(35)-C(88) carbon cage and not f-orbital lanthanide electronic metal cluster (A(3)N)(6+) orbital participation.
authors.affiliation: Department of Chemistry, Virginia Polytechnic Institute and State University, Blacksburg, Virginia 24061, USA.
authors.forename: Wujun
authors.initials: W
authors.lastname: Fu
authors.forename: Jianyuan
authors.initials: J
authors.lastname: Zhang
authors.forename: Hunter
authors.initials: H
authors.lastname: Champion
authors.forename: Tim
authors.initials: T
authors.lastname: Fuhrer
authors.forename: Hugo
authors.initials: H
authors.lastname: Azuremendi
authors.forename: Tianming
authors.initials: T
authors.lastname: Zuo
authors.forename: Jianfei
authors.initials: J
authors.lastname: Zhang
authors.forename: Kim
authors.initials: K
authors.lastname: Harich
authors.forename: Harry C
authors.initials: HC
authors.lastname: Dorn
mesh_terms: D002247:Carbon Isotopes; D002851:Chromatography, High Pressure Liquid; D018360:Crystallography, X-Ray; D004583:Electrons; D037741:Fullerenes / Q000737:chemistry / Q000302:isolation & purification; D007536:Isomerism; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure
chemical_list: D002247:Carbon Isotopes; D037741:Fullerenes