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  Investigations of the Magnetic and Spectroscopic Properties of V(III) and V(IV) Complexes

van Stappen, C., Maganas, D., DeBeer, S., Bill, E., & Neese, F. (2018). Investigations of the Magnetic and Spectroscopic Properties of V(III) and V(IV) Complexes. Inorganic Chemistry, 57(11), 6421-6438. doi:10.1021/acs.inorgchem.8b00486.

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 Creators:
van Stappen, Casey1, Author
Maganas, Dimitrios2, Author           
DeBeer, Serena1, Author
Bill, Eckhard3, Author           
Neese, Frank3, Author           
Affiliations:
1Max-Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, Mülheim an der Ruhr, 45470 North Rhine-Westphalia, Germany, ou_persistent22              
2Research Group Manganas, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541709              
3Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              

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 Abstract: Herein, we utilize a variety of physical methods including magnetometry (SQUID), electron paramagnetic resonance (EPR), and magnetic circular dichroism (MCD), in conjunction with high-level ab initio theory to probe both the ground and ligand-field excited electronic states of a series of V(IV) (S = 1/2) and V(III) (S = 1) molecular complexes. The ligand fields of the central metal ions are analyzed with the aid of ab initio ligand-field theory (AILFT), which allows for a chemically meaningful interpretation of multireference electronic structure calculations at the level of the complete-active-space self-consistent field with second-order N-electron valence perturbation theory. Our calculations are in good agreement with all experimentally investigated observables (magnetic properties, EPR, and MCD), making our extracted ligand-field theory parameters realistic. The ligand fields predicted by AILFT are further analyzed with conventional angular overlap parametrization, allowing the ligand field to be decomposed into individual σ- and π-donor contributions from individual ligands. The results demonstrate in VO2+ complexes that while the axial vanadium–oxo interaction dominates both the ground- and excited-state properties of vanadyl complexes, proximal coordination can significantly modulate the vanadyl bond covalency. Similarly, the electronic properties of V(III) complexes are particularly sensitive to the available σ and π interactions with the surrounding ligands. The results of this study demonstrate the power of AILFT-based analysis and provide the groundwork for the future analysis of vanadium centers in homogeneous and heterogeneous catalysts.

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Language(s): eng - English
 Dates: 2018-02-222018-05-232018-06-04
 Publication Status: Published in print
 Pages: 18
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.inorgchem.8b00486
 Degree: -

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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 57 (11) Sequence Number: - Start / End Page: 6421 - 6438 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669