Ho2O@C74: Ho2O Cluster Expands within a Small Non-IPR Fullerene Cage of C2(13333)-C74

Along Liu; Mingzhe Nie; Yajuan Hao; Ying Yang; Taishan Wang; Zdenek Slanina; Hailin Cong; Lai Feng; Chunru Wang; Filip Uhlik

doi:10.1021/acs.inorgchem.8b03145

Ho₂O@C₇₄: Ho₂O Cluster Expands within a Small Non-IPR Fullerene Cage of C₂(13333)-C₇₄

Inorg Chem. 2019 Apr 15;58(8):4774-4781. doi: 10.1021/acs.inorgchem.8b03145. Epub 2019 Apr 2.

Authors

Along Liu^{1

2}, Mingzhe Nie³, Yajuan Hao¹, Ying Yang¹, Taishan Wang³, Zdenek Slanina⁴, Hailin Cong², Lai Feng¹, Chunru Wang³, Filip Uhlik⁵

Affiliations

¹ College of Energy, Soochow Institute for Energy and Materials InnovationS & Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province , Soochow University , Suzhou 215006 , China.
² Laboratory for New Fiber Materials and Modern Textile, Growing Base for State Key Laboratory, College of Chemical Engineering , Qingdao University , Qingdao 266071 , China.
³ Beijing National Laboratory for Molecular Sciences, Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry , Chinese Academy of Sciences , Beijing 100190 , China.
⁴ Department of Chemistry and Biochemistry , University of Arizona , Tucson , Arizona 85721-0041 , United States.
⁵ Department of Physical and Macromolecular Chemistry, Faculty of Science , Charles University , 128 43 Prague 2 , Czech Republic.

PMID: 30938991
DOI: 10.1021/acs.inorgchem.8b03145

Abstract

Steering the cluster configuration inside a fullerene cage has been one of most interesting topics in the field of fullerenes, since the physical property of a cluster fullerene may be modified accordingly. It has been well-recognized that the cluster configuration can be tuned via altering the cage size. Typically, the carbide cluster and the oxide cluster are experimentally seen to be curled up within a small fullerene cage whereas they are expanded in a large cage. In this work, a new oxide cluster fullerene Ho₂O@ C₂(13333)-C₇₄ is prepared and isolated. The single-crystal X-ray diffraction (XRD) study reveals that the Ho₂O cluster, however, expands within the small non-IPR cage of C₂(13333)-C₇₄ with a Ho-O-Ho angle of >170°, indicating that cluster configuration is highly related to the cage shape and cage structure as well. The DFT computation demonstrates that the cluster-to-cage electron-transfer obviously enhances the aromaticity of the motif containing the fused-pentagon pair and hence stabilizes the non-IPR cage of C₂(13333)-C₇₄. In addition, the electrochemical and magnetic properties of Ho₂O@ C₂(13333)-C₇₄ are studied to further investigate the effect of endohedral Ho₂O cluster.