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New Insight into U@C80: Missing U@D3(31921)-C80 and Nuanced Enantiomers of U@C1(28324)-C80.
Inorg Chem 2019; 58(20):14159-14166IC

Abstract

Triplet U@C1(28324)-C80, violating the isolated pentagon rule, is experimentally recognized as the stable isomer for uranium-based endohedral monometallofullerene U@C80. Here we first verified that triplet U@D3(31921)-C80, following the isolated pentagon rule, was to be another thermodynamically stable isomer via density functional theory in conjunction with statistical thermodynamic analysis. U@D3(31921)-C80 was probably missing in the previous experiment and would be a promising isomer in the to-be experiment because of its excellently thermodynamic stability. In addition, the anomalous metal position was revealed in U@D3(31921)-C80 and U@C1(28324)-C80. Four-electron transfer from U to C80 was also revealed for the two isomers. Thus, two unpaired 5f electrons were still in the U for U@D3(31921)-C80 and U@C1(28324)-C80. Moreover, the covalent interactions between U and C80 in U@D3(31921)-C80 were stronger than those in U@C1(28324)-C80. The electrostatic interactions preponderated in the interaction energy ΔEint between U and C80 for U@C1(28324)-C80, and the orbital interactions dominated in the ΔEint for U@D3(31921)-C80. The electrophilic and nucleophilic reactivities were also analyzed for U@D3(31921)-C80 and U@C1(28324)-C80. Electronic circular dichroism spectra were simulated to distinguish the two enantiomers of U@C1(28324)-C80. We are hopeful that this investigation will be valuable for further identification of the two enantiomers in future experiments.

Authors+Show Affiliations

Institute for Chemical Physics & Department of Chemistry, School of Science, State Key Laboratory of Electrical Insulation and Power Equipment, and MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter , Xi'an Jiaotong University , Xi'an 710049 , China.Institute for Chemical Physics & Department of Chemistry, School of Science, State Key Laboratory of Electrical Insulation and Power Equipment, and MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter , Xi'an Jiaotong University , Xi'an 710049 , China.Institute for Molecular Science , Okazaki 444-8585 , Japan.Institute for Molecular Science , Okazaki 444-8585 , Japan.Institute for Chemical Physics & Department of Chemistry, School of Science, State Key Laboratory of Electrical Insulation and Power Equipment, and MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter , Xi'an Jiaotong University , Xi'an 710049 , China.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31596576

Citation

Zhao, Yao-Xiao, et al. "New Insight Into U@C80: Missing U@D3(31921)-C80 and Nuanced Enantiomers of U@C1(28324)-C80." Inorganic Chemistry, vol. 58, no. 20, 2019, pp. 14159-14166.
Zhao YX, Li MY, Zhao P, et al. New Insight into U@C80: Missing U@D3(31921)-C80 and Nuanced Enantiomers of U@C1(28324)-C80. Inorg Chem. 2019;58(20):14159-14166.
Zhao, Y. X., Li, M. Y., Zhao, P., Ehara, M., & Zhao, X. (2019). New Insight into U@C80: Missing U@D3(31921)-C80 and Nuanced Enantiomers of U@C1(28324)-C80. Inorganic Chemistry, 58(20), pp. 14159-14166. doi:10.1021/acs.inorgchem.9b02196.
Zhao YX, et al. New Insight Into U@C80: Missing U@D3(31921)-C80 and Nuanced Enantiomers of U@C1(28324)-C80. Inorg Chem. 2019 Oct 21;58(20):14159-14166. PubMed PMID: 31596576.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - New Insight into U@C80: Missing U@D3(31921)-C80 and Nuanced Enantiomers of U@C1(28324)-C80. AU - Zhao,Yao-Xiao, AU - Li,Meng-Yang, AU - Zhao,Pei, AU - Ehara,Masahiro, AU - Zhao,Xiang, Y1 - 2019/10/09/ PY - 2019/10/10/pubmed PY - 2019/10/10/medline PY - 2019/10/10/entrez SP - 14159 EP - 14166 JF - Inorganic chemistry JO - Inorg Chem VL - 58 IS - 20 N2 - Triplet U@C1(28324)-C80, violating the isolated pentagon rule, is experimentally recognized as the stable isomer for uranium-based endohedral monometallofullerene U@C80. Here we first verified that triplet U@D3(31921)-C80, following the isolated pentagon rule, was to be another thermodynamically stable isomer via density functional theory in conjunction with statistical thermodynamic analysis. U@D3(31921)-C80 was probably missing in the previous experiment and would be a promising isomer in the to-be experiment because of its excellently thermodynamic stability. In addition, the anomalous metal position was revealed in U@D3(31921)-C80 and U@C1(28324)-C80. Four-electron transfer from U to C80 was also revealed for the two isomers. Thus, two unpaired 5f electrons were still in the U for U@D3(31921)-C80 and U@C1(28324)-C80. Moreover, the covalent interactions between U and C80 in U@D3(31921)-C80 were stronger than those in U@C1(28324)-C80. The electrostatic interactions preponderated in the interaction energy ΔEint between U and C80 for U@C1(28324)-C80, and the orbital interactions dominated in the ΔEint for U@D3(31921)-C80. The electrophilic and nucleophilic reactivities were also analyzed for U@D3(31921)-C80 and U@C1(28324)-C80. Electronic circular dichroism spectra were simulated to distinguish the two enantiomers of U@C1(28324)-C80. We are hopeful that this investigation will be valuable for further identification of the two enantiomers in future experiments. SN - 1520-510X UR - https://www.unboundmedicine.com/medline/citation/31596576/New_Insight_into_U@C80:_Missing_U@D3(31921)-C80_and_Nuanced_Enantiomers_of_U@C1(28324)-C80 L2 - https://dx.doi.org/10.1021/acs.inorgchem.9b02196 DB - PRIME DP - Unbound Medicine ER -