Sc2O@Td 19151)-C76 : hindered cluster motion inside a tetrahedral carbon cage probed by crystallographic and computational studies

Ting Yang; Yajuan Hao; Laura Abella; Qiangqiang Tang; Xiaohong Li; Yingbo Wan; Antonio Rodríguez-Fortea; Josep M Poblet; Lai Feng; Ning Chen

doi:10.1002/chem.201500904

Sc2O@Td 19151)-C76 : hindered cluster motion inside a tetrahedral carbon cage probed by crystallographic and computational studies

Chemistry. 2015 Jul 27;21(31):11110-7. doi: 10.1002/chem.201500904. Epub 2015 Jun 18.

Authors

Affiliations

¹ Laboratory of Advanced Optoelectronic Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu, 212163 (China).
² College of Physics, Optoelectronics and Energy and Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215006 (China).
³ Departament de Química Física i Inorgànica, Universitat Rovira i Virgili c/Marcel⋅lí Domingo 1, 43007 Tarragona (Spain).
⁴ Departament de Química Física i Inorgànica, Universitat Rovira i Virgili c/Marcel⋅lí Domingo 1, 43007 Tarragona (Spain). [email protected].
⁵ Departament de Química Física i Inorgànica, Universitat Rovira i Virgili c/Marcel⋅lí Domingo 1, 43007 Tarragona (Spain). [email protected].
⁶ College of Physics, Optoelectronics and Energy and Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215006 (China). [email protected].
⁷ Laboratory of Advanced Optoelectronic Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu, 212163 (China). [email protected].

PMID: 26088830
DOI: 10.1002/chem.201500904

Abstract

A new cluster fullerene, Sc2 O@Td (19151)-C76 , has been isolated and characterized by mass spectrometry, UV/Vis/NIR absorption, (45) Sc NMR spectroscopy, cyclic voltammetry, and single-crystal X-ray diffraction. The crystallographic analysis unambiguously assigned the cage structure as Td (19151)-C76 , which is the first tetrahedral fullerene cage characterized by single-crystal X-ray diffraction. This study also demonstrated that the Sc2 O cluster has a much smaller ScOSc angle than that of Sc2 O@Cs (6)-C82 and the Sc2 O unit is fully ordered inside the Td (19151)-C76 cage. Computational studies further revealed that the cluster motion of the Sc2 O is more restrained in the Td (19151)-C76 cage than that in the Cs (6)-C82 cage. These results suggest that cage size affects not only the shapes but also the cluster motion inside fullerene cages.

Keywords: cage compounds; carbon; cluster compounds; fullerenes; scandium.