Favorite Orientation of the Carbon Cage and a Unique Two-Dimensional-Layered Packing Model in the Cocrystals of Nd@C82(I,II) Isomers with Decapyrrylcorannulene

Yu Zhang; Runnan Guan; Muqing Chen; Yongpeng Shen; Qingjiang Pan; Yongfu Lian; Shangfeng Yang

doi:10.1021/acs.inorgchem.0c02744

Favorite Orientation of the Carbon Cage and a Unique Two-Dimensional-Layered Packing Model in the Cocrystals of Nd@C₈₂(I,II) Isomers with Decapyrrylcorannulene

Inorg Chem. 2021 Feb 1;60(3):1462-1471. doi: 10.1021/acs.inorgchem.0c02744. Epub 2021 Jan 13.

Authors

Yu Zhang^{1

2}, Runnan Guan², Muqing Chen², Yongpeng Shen¹, Qingjiang Pan¹, Yongfu Lian¹, Shangfeng Yang²

Affiliations

¹ Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, China.
² Hefei National Laboratory for Physical Sciences at Microscale, CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, and Anhui Laboratory of Advanced Photon Science and Technology, University of Science and Technology of China, Hefei 230026, China.

PMID: 33439637
DOI: 10.1021/acs.inorgchem.0c02744

Abstract

To date, the experimental studies on Nd-based metallofullerenes are only limited to spectroscopic characterizations. In this work, the molecular structures of Nd@C₈₂(I,II) isomers, including the isomeric symmetry of the C cage and the position of endohedral Nd atom, as well as their unique two-dimensional (2D)-layered crystallographic packing structures were initially and unambiguously elucidated, based on the X-ray structural analyses of the cocrystals of Nd@C₈₂(I) or Nd@C₈₂(II) with cocrystallizing agent decapyrrylcorannulene (DPC). In the V-shaped unit cell, the endohedral Nd atom prefers a site as far away from the DPC molecules as possible because of the unevenly distributed charge on the C cage mainly related to the charge transfers from the endohedral Nd atom, cocrystallizing agent DPC, and solvent toluene molecules to the C₈₂ cage. Apart from charge transfers, multiple C-H···π intermolecular interactions are also confirmed to play important roles both for the orientation of the C cage correlated with the preferential sites of the endohedral Nd atom and for the 2D-layered packing structures within the cocrystals. Density functional theory computations offered theoretical support for the molecular structures of Nd@C₈₂(I,II) isomers, the valence of the endohedral Nd atom (between II+ and III+), and the global ground state, i.e., the Nd@C_2v(9)-C₈₂ isomer in the quintet state.