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Co13O8—metalloxocubes:a new class of perovskite-like neutral clusters with cubic aromaticity

National Science Review 2021年第1期8卷 89-97页

作者： Lijun Geng Mouyi Weng Cong-Qiao Xu Hanyu Zhang Chaonan Cui Haiming Wu Xin Chen Mingyu Hu Hai Lin Zhen-Dong Sun Xi Wang Han-Shi Hu Jun Li Jiaxin Zheng Zhixun Luo Feng Pan Jiannian Yao Beijing National Laboratory for Molecular Sciences (BNLMS) State Key Laboratory for Structural Chemistry of Unstable and Stable Species Institute of Chemistry Chinese Academy of Sciences School of Physics Shandong University School of Advanced Materials Peking University Shenzhen Graduate School Department of Chemistry Southern University of Science and Technology University of Chinese Academy of Sciences School of Physics and Electrical Engineering Kashi University College of Science Beijing Jiaotong University Department of Chemistry and Key Laboratory of Organic Optoelectronics and Molecular Engineering of Ministry of Education Tsinghua University

Exploring stable clusters to understand structural evolution from atoms to macroscopic matter and to construct new materials is interesting yet challenging in chemistry. Utilizing our newly developed deep-ultraviolet laser ionization mass spectrometry technique, here we observe the reactions of neutral cobalt clusters with oxygen and find a very stable cluster species of Co13O8that dominates the mass distribution in the presence of a large flow rate of oxygen gas. The results of global-minimum structural search reveal a unique cubic structure and distinctive stability of the neutral Co13O8cluster that forms a new class of metal oxides that we named as ‘metalloxocubes’. Thermodynamics and kinetics calculations illustrate the structural evolution from icosahedral Co13to the metalloxocube Co13O8with decreased energy, enhanced stability and aromaticity. This class of neutral oxygen-passivated metal clusters may be an ideal candidate for genetic materials because of the cubic nature of the building blocks and the stability due to cubic aromaticity.

关键词： metalloxocube oxygen-passivated metal cluster cubic aromaticity cluster materials magnetic property

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