Understanding the Electronic Structure and Stability of BnXn0/2– (n = 4, 6; X = H, F, Cl, Br, I, At, Ts) Clusters†
Ruo-Ya Wang
Henan Key Laboratory of Boron Chemistry and Advanced Energy Materials, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan, 453007 China
Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong, 518055 China
Search for more papers by this authorJing-Xuan Zhang
Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong, 518055 China
Search for more papers by this authorXue-Lian Jiang
Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong, 518055 China
Search for more papers by this authorNana Ma
Henan Key Laboratory of Boron Chemistry and Advanced Energy Materials, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan, 453007 China
Search for more papers by this authorXuenian Chen
Henan Key Laboratory of Boron Chemistry and Advanced Energy Materials, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan, 453007 China
Green Catalysis Center and College of Chemistry, Zhengzhou University, Zhengzhou, Henan, 450001 China
Search for more papers by this authorCorresponding Author
Cong-Qiao Xu
Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong, 518055 China
E-mail: [email protected]Search for more papers by this authorJun Li
Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong, 518055 China
Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing, 100084 China
Search for more papers by this authorRuo-Ya Wang
Henan Key Laboratory of Boron Chemistry and Advanced Energy Materials, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan, 453007 China
Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong, 518055 China
Search for more papers by this authorJing-Xuan Zhang
Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong, 518055 China
Search for more papers by this authorXue-Lian Jiang
Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong, 518055 China
Search for more papers by this authorNana Ma
Henan Key Laboratory of Boron Chemistry and Advanced Energy Materials, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan, 453007 China
Search for more papers by this authorXuenian Chen
Henan Key Laboratory of Boron Chemistry and Advanced Energy Materials, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan, 453007 China
Green Catalysis Center and College of Chemistry, Zhengzhou University, Zhengzhou, Henan, 450001 China
Search for more papers by this authorCorresponding Author
Cong-Qiao Xu
Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong, 518055 China
E-mail: [email protected]Search for more papers by this authorJun Li
Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong, 518055 China
Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing, 100084 China
Search for more papers by this author†Dedicated to Department of Chemistry, SUSTech, on the Occasion of Her 10th Anniversary.
Main observation and conclusion
Borane clusters and their derivatives have attracted extensive attention in inorganic chemistry due to their fascinating multi-center bonding patterns and physicochemical properties. Here we report a systematic theoretical investigation on the geometry, electronic structure and chemical bonding of BnXn0/2- (n = 4, 6; X = H, F, Cl, Br, I, At, Ts) clusters, attempting to explore their bonding features, exceptional stability and the ligand effect. We find that the electronic structure and stability of BnXn0/2- clusters can be tuned by the size of the boron cage and electronegativity of the ligand. Fragment orbital energy matching and orbital overlap are of great importance to the covalency of the cluster. In addition to the ionic electrostatic interaction that dominates the bonding interaction and decreases as the ligand becomes heavier, multi-center bonding covalency determined by the orbital interaction increases accordingly, attributing to the reducing electronegativity. The σ-donations from the ligand to the boron cage as well as multi-center two-electron (nc-2e) bonding contribute to the σ aromaticity and superb stability. This work reveals the foremost factors that determine the structure and stability of boron clusters, and provides insights into the nature of chemical bonding for species with boron cages and even bulk boron.
Supporting Information
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Appendix S1: Supporting Information |
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