The State of Asymmetric Nitride Clusters in Endohedral Fullerenes as Studied by N-14 NMR Spectroscopy: Experiment and Theory

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Alexey A. Popov - , Leibniz Institute for Solid State and Materials Research Dresden, Lomonosov Moscow State University (Author)
  • Sandra Schiemenz - , Leibniz Institute for Solid State and Materials Research Dresden (Author)
  • Stanislav M. Avdoshenko - , TUD Dresden University of Technology (Author)
  • Shangfeng Yang - , Leibniz Institute for Solid State and Materials Research Dresden (Author)
  • Gianaurelio Cuniberti - , Chair of Materials Science and Nanotechnology, Austrian Academy of Sciences, Leibniz Institute of Polymer Research Dresden, Pohang University of Science and Technology, Div IT Convergence Engn, Natl Ctr Nanomat Technol (Author)
  • Lothar Dunsch - , Leibniz Institute for Solid State and Materials Research Dresden (Author)

Abstract

While the role of asymmetric nitride clusters on the cage size and symmetry in fullerene-based structures is already well-known, the role of the asymmetric arrangement of metals in nitride clusters on the nitrogen is studied in detail in this work. It is discovered that asymmetric mixed-metal nitride clusters give sufficiently narrow N-14 NMR signals to make NMR the method of choice to characterize the endohedral cluster from the inside. In the series of mixed-metal nitride clusterfullerenes LuxSc3-xN@C-80 and LuxY3-xN@C-80 (x = 0-3) the delta(N-14) values are found to be linear functions of x showing that N-14 chemical shifts are additive values with specific increment for each kind of metal atoms. Density functional theory calculations are performed to interpret the experimentally measured spectra. To reveal the main factors affecting N-14 chemical shifts in nitride clusterfullerenes, shielding tensor components are analyzed in terms of Ramsey theory both in localized and canonical molecular orbitals. N-14 chemical shifts in M3N@C-80 and related systems are shown to be determined solely by nitrogen-localized orbitals and in particular by the p(x,y,z) atomic orbitals of nitrogen. As a result, the peculiarities of the nitrogen shielding in nitride clusterfullerenes can be interpreted by the simple analysis of the nitrogen-projected density of states and its variation in different chemical environments.

Details

Original languageEnglish
Pages (from-to)15257-15265
Number of pages9
JournalJournal of Physical Chemistry C, Nanomaterials and interfaces
Volume115
Issue number31
Publication statusPublished - 11 Aug 2011
Peer-reviewedYes

External IDs

Scopus 79961212966
WOS 000293419700019

Keywords

Keywords

  • Nuclear-magnetic-resonance, Auxiliary basis-sets, Non-ipr fullerene, Carbon cage, Vibrational structure, Shielding tensors, Metal atoms, Clusterfullerenes, Epr, Metallofullerenes