Structure and bonding of [VIVO(acac)2] on the surface of AlF3 as studied by pulsed electron nuclear double resonance and hyperfine sublevel correlation spectroscopy

Literature Information

Publication Date 2009-06-10
DOI 10.1039/B903826B
Impact Factor 3.676
Authors

Vijayasarathi Nagarajan, Barbara Müller, Oksana Storcheva, Klaus Köhler, Andreas Pöppl


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Abstract

Well defined isolated [VIVO(acac)2] surface complexes have been prepared on aluminium trifluoride, α-AlF3, as solid support by equilibrium adsorption from liquid solution. The paramagnetic vanadium(IV) surface complexes were studied by pulsed electron spin resonance spectroscopy in combination with quantum chemical calculations using density functional theory. 19F and 27Al ligand hyperfine interactions with the nuclei of the AlF3 support observed by pulsed electron nuclear double resonance and hyperfine sublevel correlation spectroscopy experiments verify the direct chemical bonding between the vanadium and a surface fluorine atom. Detailed analysis of the ligand hyperfine couplings supported by quantum chemical calculations indicates that the axial position of [VIVO(acac)2]trans to the oxo ligand is bound directly to a terminal fluorine atom of the support. Analysis of the 1H ligand hyperfine interaction revealed that an acidic H+ of the AlF3 surface protonated a donor oxygen of the acetylacetone ligand in the surface complex.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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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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