EPR study of topoisomers of La@C82 and La@C90

Abstract

An analysis of the temperature dependence of the line width variation of topoisomers (I) and (II) of La@C82 revealed that both molecules exhibit practically identical rotational correlation times from room temperature down to the freezing point of CS2. Although this result indicates confinement of the metal ion, from the increased line width of13C satellites in isomer (II) we conclude that in this molecule there might be increased mobility within a confine volume. Three stable topoisomers of La@C90 were identified for the first time. One of these topoisomers was separated by HPLC technique. We were unable, however, to detect any nuclear spin dependence of the EPR line width even at low temperatures. This might indicate that in this case the ion is no longer confined to a specific binding site, although a more trivial explanation assuming small anisotropies of all hyperfine interactions cannot yet be ruled out.