Two- and Three-Electron Oxidation of Single-Site Vanadium Centers at Surfaces by Ligand Design
| Autor: | Brian J. Cook, Daniel Skomski, Christopher D. Tempas, Kenneth G. Caulton, Alexander V. Polezhaev, Steven L. Tait, Kevin A. Smith |
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| Rok vydání: | 2015 |
| Předmět: |
Ligand
Vanadium chemistry.chemical_element General Chemistry Heterogeneous catalysis Photochemistry Biochemistry Redox Catalysis law.invention Metal Tetrazine chemistry.chemical_compound Colloid and Surface Chemistry chemistry law visual_art Oxidizing agent visual_art.visual_art_medium Scanning tunneling microscope |
| Zdroj: | Journal of the American Chemical Society. 137:7898-7902 |
| ISSN: | 1520-5126 0002-7863 |
| Popis: | Rational, systematic tuning of single-site metal centers on surfaces offers a new approach to increase selectivity in heterogeneous catalysis reactions. Although such metal centers of uniform oxidation states have been achieved, the ability to control their oxidation states through the use of carefully designed ligands had not been shown. To this end, tetrazine ligands functionalized by two pyridinyl or pyrimidinyl substituents were deposited, along with vanadium metal, on the Au(100) surface. The greater oxidizing power of the bis-pyrimidinyltetrazine facilitates the on-surface redox formation of V(3+), compared to V(2+) when paired with the bis-pyridinyltetrazine, as determined by X-ray photoelectron spectroscopy. This demonstrates the ability to control metal oxidation states in surface coordination architectures by altering the redox properties of organic ligands. The metal-ligand complexes take the form of one-dimensional polymeric chains, resolved by scanning tunneling microscopy. The chain structures in the first layer are very uniform and are based on the same quasi-square-planar coordination geometry around single-site V with either ligand. Formation of a different, dimer structure is observed in the early stages of the second layer formation. These systems offer new opportunities in controlling the oxidation state of single-site transition metal atoms at a surface for new advances in heterogeneous catalysts. |
| Databáze: | OpenAIRE |
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