Steering Lu3N clusters in C76–78 cages: cluster configuration dominated by cage transformation. Issue 46 (15th November 2022)

• Record Type: Journal Article
• Authors: Yu, Pengwei; Hu, Shuaifeng; Tian, Xinyue; Shen, Wangqiang; Yu, Pengyuan; Guo, Kun; Xie, Yunpeng; Bao, Lipiao; Lu, Xing
• Is Part Of: Nanoscale. Volume 14:Issue 46(2022)
• Page Start: 17290
• Page End: 17296
• Publication Date: 2022-11-15
• Subjects: Nanoscience -- Periodicals; Nanotechnology -- Periodicals; 620.505
• DOI: 10.1039/d2nr05049h
• Languages: English
• ISSNs: 2040-3364

Abstract

Abstract : How cage transformation interacts with cluster configuration has been elucidated by three designed metallofullerenes, namely Lu3 N@ C s (17 490)-C76, Lu3 N@ C 2 (22 010)-C78, and Lu3 N@ D 3 h (5)-C78, with an easy-to-compare cluster configuration and cage arrangement. Abstract : While the strong interaction between the internal unit and the fullerene cage inside metallofullerenes is widely acknowledged, how the cage transformation interacts with the cluster configuration remains elusive. For this purpose, we herein synthesized three metallofullerene molecules with an easy-to-compare cluster configuration and cage arrangement, namely Lu3 N@ C s (17 490)-C76, Lu3 N@ C 2 (22 010)-C78, and Lu3 N@ D 3 h (5)-C78 . The three lutetium-based nitride clusterfullerenes (NCFs) with small C76–78 carbon cages were synthesized by a modified arc-discharge method and their structures were unambiguously confirmed by X-ray crystallography. Notably, the cage transformation from C s (17 490)-C76 to C 2 (22 010)-C78 via a simple C 2 -unit insertion leads to a remarkable configuration change of the encapsulated Lu3 N cluster from an unusual asymmetric plane to a common symmetric one. This close correlation between the cluster configuration and cage transformation is further confirmed by the pyramidal Lu3 N cluster in Lu3 N@ D 3 h (5)-C78 other than the symmetric planar Lu3 N unit in Lu3 N@ C 2 (22 010)-C78, as a result of an even larger difference in the cage arrangement. Astonishingly, such a cluster shrinkage, accompanied by an increase in the cage size from C s (17 490)-C76 to D 3 h (5)-C78, is dramatically opposite to the cluster expansion with cage elongation found in La2 C2 - or Y2 C2 -based metallofullerenes.