Ligand-Induced Tuning of the Electronic Structure of Rhombus Tetraboron Cluster

Ya Zhao; Tiantong Wang; Chong Wang; Zhaoyan Zhang; Huijun Zheng; Shuai Jiang; Wenhui Yan; Hua Xie; Gang Li; Jiayue Yang; Guorong Wu; Weiqing Zhang; Dongxu Dai; Xiucheng Zheng; Hongjun Fan; Ling Jiang; Xueming Yang; Mingfei Zhou

doi:10.1002/cphc.202200060

Ligand-Induced Tuning of the Electronic Structure of Rhombus Tetraboron Cluster

Chemphyschem. 2022 May 4;23(9):e202200060. doi: 10.1002/cphc.202200060. Epub 2022 Mar 16.

Authors

Ya Zhao^{1

2}, Tiantong Wang^{2

3}, Chong Wang^{2

3}, Zhaoyan Zhang^{2

3}, Huijun Zheng^{2

3}, Shuai Jiang^{1

2}, Wenhui Yan^{2

3}, Hua Xie², Gang Li², Jiayue Yang², Guorong Wu², Weiqing Zhang², Dongxu Dai², Xiucheng Zheng¹, Hongjun Fan², Ling Jiang², Xueming Yang^{2

4}, Mingfei Zhou⁵

Affiliations

¹ College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China.
² State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
³ University of Chinese Academy of Sciences, 19 A Yuquan Road, Beijing, 100049, China.
⁴ Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055, China.
⁵ Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, 200433, China.

PMID: 35294798
DOI: 10.1002/cphc.202200060

Abstract

A neutral boron carbonyl complex B₄ (CO)₃ is generated in the gas phase and is characterized by infrared plus vacuum ultraviolet (IR+VUV) two-color ionization spectroscopy and quantum chemical calculations. The complex is identified to have a planar C_2v structure with three CO ligands terminally coordinated to a rhombus B₄ core. It has a closed-shell singlet ground state that correlates to an excited state of B₄ . Bonding analyses on B₄ (CO)₃ as well as the previously reported B₄ and B₄ (CO)₂ indicate that the electronic structure of rhombus tetraboron cluster changes from a close-shell singlet to an open-shell singlet in B₄ (CO)₂ and to a close-shell singlet in B₄ (CO)₃ , demonstrating that the electronic structures of boron clusters can be effectively tuned via sequential CO ligand coordination.

Keywords: bond theory; carbon monoxide; cluster compound; electronic structure; infrared spectroscopy.

Abstract

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