An oxygen-passivated vanadium cluster [V@V10O15]− with metal–metal coordination produced by reacting Vn− with O2

Literature Information

Publication Date 2020-12-08
DOI 10.1039/D0CP05385F
Impact Factor 3.676
Authors

Miao Yan, Si-Dian Li


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Abstract

Vanadium cluster anions are highly reactive making the preparation of pure Vn− and the observation of their reactivity extremely challenging. Herein, well-resolved anionic Vn− clusters are prepared enabling an in-depth study on their reactions with O2 in the gas phase. While pure metal clusters of a magic number are not identified due to the strong V–O bonding, interestingly an unexpected oxide V11O15− was experimentally observed in surviving O2 etching reactions. First-principles theory calculations indicate that V11O15− possesses a body-centered pentagonal prism structure (D5h, ), with the V@V10 core fully protected by 15 oxygen bridges. Such an oxygen-protected metal cluster [V@V10O15]− exhibits typical superatom orbital features pertaining to the V@V10 core which shows effective metal–metal coordination bonding. Meanwhile, the high stability of [V@V10O15]− is reinforced by the V–O–V conjugation interactions which help to maintain the structural integrity, resulting in 3D inorganic aromaticity. This finding of such an oxygen-passivated superatom cluster sheds light on the bonding nature in ligand-protected metal clusters via wet synthesis.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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