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Isolation and Crystallographic Characterization of Lu 3 N@C 2 n (2 n =80–88): Cage Selection by Cluster Size
Author(s) -
Shen WangQiang,
Bao LiPiao,
Hu ShuaiFeng,
Gao XueJiao,
Xie YunPeng,
Gao XingFa,
Huang WenHuan,
Lu Xing
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201804651
Subject(s) - lutetium , ionic radius , crystallography , cluster (spacecraft) , cage , metal , chemistry , materials science , ion , mathematics , organic chemistry , combinatorics , computer science , yttrium , programming language , oxide
The small Sc 3 N cluster has only been found in such small cages as C 2 n (2 n =68, 78, 80, 82), whereas the large M 3 N (M=Y, Gd, Tb, Tm) clusters choose those larger cages C 2 n (2 n =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 Lu 3 N@ I h (7)‐C 80 , Lu 3 N@ D 5 h (6)‐C 80 , Lu 3 N@ C 2 v (9)‐C 82 , Lu 3 N@ C s (51365)‐C 84 , Lu 3 N@ D 3 (17)‐C 86 , and Lu 3 N@ D 2 (35)‐C 88 by single‐crystal X‐ray diffraction crystallography. It was confirmed that the encaged Lu 3 N cluster always adopts a planar geometry in Lu 3 N@C 80‐88 isomers to ensure substantial metal‐cage/metal‐nitrogen interactions. As a result, the Lu 3 N cluster selects the C 2 v (9)‐C 82 cage, which also encapsulates Sc 3 N, instead of the C s (39663)‐C 82 cage which is more suitable for M 3 N (M=Y, Gd, Tb, Tm). However, different from Sc 3 N, Lu 3 N can also template the C 84–88 cages which are absent for Sc 3 N‐containing EMFs, confirming clearly the size effect of the internal cluster on selecting the outer cage.