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Redox-active ligand controlled selectivity of vanadium oxidation on Au(100)

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Abstract

Metal–organic coordination networks at surfaces, formed by on-surface redox assembly, are of interest for designing specific and selective chemical function at surfaces for heterogeneous catalysts and other applications. The chemical reactivity of single-site transition metals in on-surface coordination networks, which is essential to these applications, has not previously been fully characterized. Here, we demonstrate with a surface-supported, single-site V system that not only are these sites active toward dioxygen activation, but the products of that reaction show much higher selectivity than traditional vanadium nanoparticles, leading to only one V-oxo product. We have studied the chemical reactivity of one-dimensional metal–organic vanadium – 3,6-di(2-pyridyl)-1,2,4,5-tetrazine (DPTZ) chains with O2. The electron-rich chains self-assemble through an on-surface redox process on the Au(100) surface and are characterized by X-ray photoelectron spectroscopy, scanning tunneling microscopy, high-resolution electron energy loss spectroscopy, and density functional theory. Reaction of V-DPTZ chains with O2 causes an increase in V oxidation state from VII to VIV, resulting in a single strongly bonded (DPTZ2−)VIVO product and spillover of O to the Au surface. DFT calculations confirm these products and also suggest new candidate intermediate states, providing mechanistic insight into this on-surface reaction. In contrast, the oxidation of ligand-free V is less complete and results in multiple oxygen-bound products. This demonstrates the high chemical selectivity of single-site metal centers in metal–ligand complexes at surfaces compared to metal nanoislands.

Graphical abstract: Redox-active ligand controlled selectivity of vanadium oxidation on Au(100)

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Publication details

The article was received on 02 Nov 2017, accepted on 02 Jan 2018 and first published on 04 Jan 2018


Article type: Edge Article
DOI: 10.1039/C7SC04752E
Citation: Chem. Sci., 2018, Advance Article
  • Open access: Creative Commons BY-NC license
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    Redox-active ligand controlled selectivity of vanadium oxidation on Au(100)

    C. D. Tempas, Tobias W. Morris, D. L. Wisman, D. Le, N. U. Din, C. G. Williams, M. Wang, A. V. Polezhaev, T. S. Rahman, K. G. Caulton and S. L. Tait, Chem. Sci., 2018, Advance Article , DOI: 10.1039/C7SC04752E

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