Abstract
The small Sc3 N cluster has only been found in such small cages as C2n (2n=68, 78, 80, 82), whereas the large M3 N (M=Y, Gd, Tb, Tm) clusters choose those larger cages C2n (2n=82-88). Herein, concrete experimental evidence is presented to establish the size effect of the internal metallic cluster on selecting the outer cage of endohedral metallofullerenes (EMFs) by using a medium-sized metal, lutetium, which possesses an ionic radius between Sc and Gd. A series of lutetium-containing EMFs have been obtained and their structures are unambiguously determined as Lu3 N@Ih (7)-C80 , Lu3 N@D5h (6)-C80 , Lu3 N@C2v (9)-C82 , Lu3 N@Cs (51365)-C84 , Lu3 N@D3 (17)-C86 , and Lu3 N@D2 (35)-C88 by single-crystal X-ray diffraction crystallography. It was confirmed that the encaged Lu3 N cluster always adopts a planar geometry in Lu3 N@C80-88 isomers to ensure substantial metal-cage/metal-nitrogen interactions. As a result, the Lu3 N cluster selects the C2v (9)-C82 cage, which also encapsulates Sc3 N, instead of the Cs (39663)-C82 cage which is more suitable for M3 N (M=Y, Gd, Tb, Tm). However, different from Sc3 N, Lu3 N can also template the C84-88 cages which are absent for Sc3 N-containing EMFs, confirming clearly the size effect of the internal cluster on selecting the outer cage.
Published Version
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