[CpNi(diselenolene)] Neutral Radical Complexes: Electron Paramagnetic Resonance and Density Functional Theory Investigations

Grosshans, Philippe; Adkine, Prashant Madhukar; Sidorenkova Cruz Gonzalez, Elena; Nomura, Mitsushiro; Fourmigué, Marc; Geoffroy, Michel

doi:10.1021/jp800584v

Scientific article

English

[CpNi(diselenolene)] Neutral Radical Complexes: Electron Paramagnetic Resonance and Density Functional Theory Investigations

Contributors

Grosshans, Philippe; Adkine, Prashant Madhukar; Sidorenkova Cruz Gonzalez, Elena; Nomura, Mitsushiro; Fourmigué, Marc; Geoffroy, Michel

Published in

The journal of physical chemistry. A, vol. 112, no. 17, p. 4067-4073

Publication date

2008

Abstract

77Se-enriched CpNi(bds) (bds = 1,2-benzenediselenolate), has been synthesized and its g tensor and 77Se hyperfine tensors have been obtained from its frozen solution electron paramagnetic resonance (EPR) spectrum. These parameters are consistent with those calculated by density functional theory (DFT); it is shown that 10% of the spin is localized on each selenium and that the direction associated to the maximum 77Se couplings is aligned along the gmin direction, perpendicular to the Ni(bds) plane. EPR measurements and DFT calculations are also carried out on the 77Se enriched complex CpNi(dsit) as well on the two dithiolene analogues CpNi(bdt) and CpNi(dmit). The optimized structures of the isolated CpNi(bds) and CpNi(bdt) complexes have been used to generate the idealized dimers (bds)NiCp···CpNi(bds) and (bdt)NiCp···CpNi(bdt) characterized by Cp···Cp overlap. The exchange parameters J calculated at the DFT level for these systems are in reasonable accord with the experimental values. The influence of the geometry of the dimer on its magnetic properties is assessed by calculating the variation of J as a function of the relative orientation of the two Ni(diselenolene) or Ni(dithiolene) planes.

UNIGE affiliation entities

Faculté des sciences / Section de chimie et biochimie / Département de chimie physique

UNIGE research groups

Groupe Geoffroy

Citation (ISO format)

GROSSHANS, Philippe et al. [CpNi(diselenolene)] Neutral Radical Complexes: Electron Paramagnetic Resonance and Density Functional Theory Investigations. In: The journal of physical chemistry. A, 2008, vol. 112, n° 17, p. 4067–4073. doi: 10.1021/jp800584v

Article (Published version)

Identifiers

PID : unige:3574
DOI : 10.1021/jp800584v

Additional URL for this publication

http://pubs.acs.org/cgi-bin/article.cgi/jpcafh/2008/112/i17/pdf/jp800584v.pdf

Journal ISSN

1089-5639

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02/10/2009 15:18:22

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14/03/2023 15:15:26

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14/03/2023 15:15:26

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10/06/2025 21:30:11

[CpNi(diselenolene)] Neutral Radical Complexes: Electron Paramagnetic Resonance and Density Functional Theory Investigations

Contributors

Published in

Publication date

Abstract

UNIGE affiliation entities

UNIGE research groups

Citation (ISO format)

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Additional URL for this publication

Journal ISSN

Technical informations

Creation

First validation

Update

Status update

Last indexation