title: Deviation from the planarity--a large Dy3N cluster encapsulated in an Ih-C80 cage: an X-ray crystallographic and vibrational spectroscopic study.
abstract: The high-yield synthesis of Dy3N@C80 (I) opens the possibility of characterizing its molecular and vibrational structures. We report on the structure determination of Dy3N@C80 (I) by X-ray crystallographic study of single crystal of Dy3N@C80.Ni(OEP).2C6H6, revealing a nearly planar Dy3N cluster encapsulated in an Ih-C80 cage. The vibrational structure of Dy3N@C80 (I) is studied by Fourier transform infrared (FTIR) and Raman spectroscopy in combination with force-field calculations. A correlation was found between the antisymmetric metal-nitrogen stretching vibration and the structure of the M3N cluster of M3N@C80 (I) (M = Y, Gd, Tb, Dy, Ho, Er, Tm). Moreover, a stronger interaction between the encaged nitride cluster and the C80 carbon cage was found in the class II M3N@C80 (I) (M = Y, Gd, Tb, Dy, Ho, Er, Tm) than in Sc3N@C80 (I). This study demonstrates that the cluster size plays the dominating role in the structure of the M3N cluster in M3N@C80 (I).
authors.affiliation: Group of Electrochemistry and Conducting Polymers, Leibniz-Institute for Solid State and Materials Research (IFW) Dresden, D-01171 Dresden, Germany. s.yang@ifw-dresden.de
authors.forename: Shangfeng
authors.initials: S
authors.lastname: Yang
authors.forename: Sergey I
authors.initials: SI
authors.lastname: Troyanov
authors.forename: Alexey A
authors.initials: AA
authors.lastname: Popov
authors.forename: Matthias
authors.initials: M
authors.lastname: Krause
authors.forename: Lothar
authors.initials: L
authors.lastname: Dunsch
mesh_terms: D018360:Crystallography, X-Ray; D004419:Dysprosium / Q000737:chemistry*; D037741:Fullerenes / Q000737:chemistry*; D008958:Models, Molecular; D009532:Nickel / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D012680:Sensitivity and Specificity; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods; D013059:Spectrum Analysis, Raman / Q000379:methods*; D013997:Time Factors; D014732:Vibration
chemical_list: D037741:Fullerenes; D009942:Organometallic Compounds; D004419:Dysprosium; D009532:Nickel