Observation of Aromatic Three-Membered Rings in Ge3C and Ge3O via Photoelectron Spectroscopy and Theoretical Calculations

Li-Juan Zhao; Shuai-Ting Yan; Hong-Guang Xu; Xi-Ling Xu; Wei-Jun Zheng

doi:10.1021/acs.inorgchem.1c02540

Observation of Aromatic Three-Membered Rings in Ge₃C and Ge₃O via Photoelectron Spectroscopy and Theoretical Calculations

Inorg Chem. 2021 Nov 1;60(21):16645-16651. doi: 10.1021/acs.inorgchem.1c02540. Epub 2021 Oct 18.

Authors

Li-Juan Zhao^{1

2}, Shuai-Ting Yan^{1

2}, Hong-Guang Xu^{1

2}, Xi-Ling Xu^{1

2}, Wei-Jun Zheng^{1

2}

Affiliations

¹ Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
² University of Chinese Academy of Sciences, Beijing 100049, China.

PMID: 34661398
DOI: 10.1021/acs.inorgchem.1c02540

Abstract

The structures and chemical bonding of Ge₃C^- and Ge₃O^- as well as their neutrals are explored with anion photoelectron spectroscopy and theoretical calculations. The vertical detachment energies of Ge₃C^- and Ge₃O^- are measured to be 1.51 ± 0.04 and 2.00 ± 0.04 eV, respectively. It is found that Ge₃C^-/0 have a C_2v symmetric planar structure with the C atom interacting with three Ge atoms. Ge₃O^-/0 have the O atom interacting with two Ge atoms of the triangular Ge₃ unit. Ge₃O^- has a C_s symmetric nonplanar structure, while Ge₃O has a C_2v symmetric planar structure. Theoretical results show that the multiconfigurational effects in Ge₃C^-/0 and Ge₃O^-/0 are insignificant. Chemical bonding analyses reveal that there exist the C-Ge₃ π_⊥ orbital interaction and two π aromatic Ge₂C units in Ge₃C. There are O-Ge₃ π_⊥ orbital interaction and one doubly aromatic Ge₃ unit in Ge₃O, but the π_⊥ orbital interaction is relatively weak.