Diamagnetic Clusters of Paramagnetic Endometallofullerenes: A Solid-State MAS NMR Study

Autor: Vyacheslav P. Bubnov, Henrike Heise, Vitaly K. Koltover, and Vera P. Lodygina, Ivan E. Kareev, Alexander Pines, John W. Logan, Yakov I. Estrin
Rok vydání: 2004
Předmět:
Zdroj: The Journal of Physical Chemistry B. 108:12450-12455
ISSN: 1520-5207
1520-6106
DOI: 10.1021/jp048610z
Popis: Solid powder samples of complexes of the endometallofullerenes (EMF) La@C82 and Y@C82 with hexamethylphosphoramide (HMPA) were studied by magic-angle spinning (MAS) NMR. We have obtained well-resolved 31P NMR spectra and 13C NMR spectra for both La-EMF/HMPA and Y-EMF/HMPA and 139La spectra for the La-EMF/HMPA. The 31P measurements on La-EMF/HMPA and Y-EMF/HMPA have revealed considerable chemical shifts of 31P signals relative to pure HMPA. Two-dimensional exchange 31P experiments revealed that HMPA molecules at different sites in the EMF/HMPA complex do not change positions at a time scale of up to 1 s. Both EMF samples demonstrate a vast chemical shift range for 31P of the bound HMPA molecules. In addition, the La-EMF/HMPA exhibits the enormous spreading of the chemical shifts for 139La. The experimental results suggest that paramagnetic La@C82 and Y@C82 in the solid state form clusters (nanoparticles) in which the exchange coupling of the EMF takes place with quenching of the most electron spins.
Databáze: OpenAIRE