Bromine as a Partial Oxidant. Oxidation State and Charge Transport in Brominated Nickel and Palladium Bis(diphenylglyoximates). A Comparison with the Iodinated Materials and Resonance Raman Structure-Spectra Correlation for Polybromides

Davida W. Kalina, Tobin J. Marks, Joseph W. Lyding, Mark T. Ratajack, Carl R. Kannewurf

Research output: Contribution to journalArticle

Abstract

This paper presents an investigation of oxidation state and charge transport in the low-dimensional materials Ni(dpg)2Br10 and Pd(dpg)2Bru, dpg = diphenylglyoximato. Resonance Raman structure-spectra correlations are discussed for polybromides, and Br5” is assigned as the predominant halogen species in both of these materials. Thus, the M(dpg)2 units are formally in fractional oxidation states of ca. +0.20 (2) (M = Ni) and +0.22 (2) (M = Pd). In the optical spectra of both materials, a broad transition at 500 nm is related to the polybromide chains. Four-probe single crystal electrical conductivities (dc) in the stacking direction at 300 K are as high as 9.1 X 10~1 234 5(cm)-1 (Ni(dpg)2BrL0) and 1.5 X -4 (cm)-1 (Pd(dpg)2Bru) The conductivity is demonstrated to be thermally activated with activation energies of 0.33 and 0.21 eV, respectively. The transport properties of the brominated materials are found to be very similar to those of the related M(dpg)2I materials (M = Ni, Pd), a result contrary to expectations if the halogen chains were the major charge carrier.

Original languageEnglish (US)
Pages (from-to)7854-7862
Number of pages9
JournalJournal of the American Chemical Society
Volume102
Issue number27
DOIs
StatePublished - Dec 1980
Externally publishedYes

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Bromine
Halogens
bromine
palladium
Palladium
Nickel
Oxidants
oxidant
Charge transfer
nickel
oxidation
Oxidation
Electric Conductivity
halogen
Charge carriers
stacking
activation energy
Transport properties
electrical conductivity
conductivity

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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title = "Bromine as a Partial Oxidant. Oxidation State and Charge Transport in Brominated Nickel and Palladium Bis(diphenylglyoximates). A Comparison with the Iodinated Materials and Resonance Raman Structure-Spectra Correlation for Polybromides",
abstract = "This paper presents an investigation of oxidation state and charge transport in the low-dimensional materials Ni(dpg)2Br10 and Pd(dpg)2Bru, dpg = diphenylglyoximato. Resonance Raman structure-spectra correlations are discussed for polybromides, and Br5” is assigned as the predominant halogen species in both of these materials. Thus, the M(dpg)2 units are formally in fractional oxidation states of ca. +0.20 (2) (M = Ni) and +0.22 (2) (M = Pd). In the optical spectra of both materials, a broad transition at 500 nm is related to the polybromide chains. Four-probe single crystal electrical conductivities (dc) in the stacking direction at 300 K are as high as 9.1 X 10~1 234 5(cm)-1 (Ni(dpg)2BrL0) and 1.5 X -4 (cm)-1 (Pd(dpg)2Bru) The conductivity is demonstrated to be thermally activated with activation energies of 0.33 and 0.21 eV, respectively. The transport properties of the brominated materials are found to be very similar to those of the related M(dpg)2I materials (M = Ni, Pd), a result contrary to expectations if the halogen chains were the major charge carrier.",
author = "Kalina, {Davida W.} and Marks, {Tobin J.} and Lyding, {Joseph W.} and Ratajack, {Mark T.} and Kannewurf, {Carl R.}",
year = "1980",
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T1 - Bromine as a Partial Oxidant. Oxidation State and Charge Transport in Brominated Nickel and Palladium Bis(diphenylglyoximates). A Comparison with the Iodinated Materials and Resonance Raman Structure-Spectra Correlation for Polybromides

AU - Kalina, Davida W.

AU - Marks, Tobin J.

AU - Lyding, Joseph W.

AU - Ratajack, Mark T.

AU - Kannewurf, Carl R.

PY - 1980/12

Y1 - 1980/12

N2 - This paper presents an investigation of oxidation state and charge transport in the low-dimensional materials Ni(dpg)2Br10 and Pd(dpg)2Bru, dpg = diphenylglyoximato. Resonance Raman structure-spectra correlations are discussed for polybromides, and Br5” is assigned as the predominant halogen species in both of these materials. Thus, the M(dpg)2 units are formally in fractional oxidation states of ca. +0.20 (2) (M = Ni) and +0.22 (2) (M = Pd). In the optical spectra of both materials, a broad transition at 500 nm is related to the polybromide chains. Four-probe single crystal electrical conductivities (dc) in the stacking direction at 300 K are as high as 9.1 X 10~1 234 5(cm)-1 (Ni(dpg)2BrL0) and 1.5 X -4 (cm)-1 (Pd(dpg)2Bru) The conductivity is demonstrated to be thermally activated with activation energies of 0.33 and 0.21 eV, respectively. The transport properties of the brominated materials are found to be very similar to those of the related M(dpg)2I materials (M = Ni, Pd), a result contrary to expectations if the halogen chains were the major charge carrier.

AB - This paper presents an investigation of oxidation state and charge transport in the low-dimensional materials Ni(dpg)2Br10 and Pd(dpg)2Bru, dpg = diphenylglyoximato. Resonance Raman structure-spectra correlations are discussed for polybromides, and Br5” is assigned as the predominant halogen species in both of these materials. Thus, the M(dpg)2 units are formally in fractional oxidation states of ca. +0.20 (2) (M = Ni) and +0.22 (2) (M = Pd). In the optical spectra of both materials, a broad transition at 500 nm is related to the polybromide chains. Four-probe single crystal electrical conductivities (dc) in the stacking direction at 300 K are as high as 9.1 X 10~1 234 5(cm)-1 (Ni(dpg)2BrL0) and 1.5 X -4 (cm)-1 (Pd(dpg)2Bru) The conductivity is demonstrated to be thermally activated with activation energies of 0.33 and 0.21 eV, respectively. The transport properties of the brominated materials are found to be very similar to those of the related M(dpg)2I materials (M = Ni, Pd), a result contrary to expectations if the halogen chains were the major charge carrier.

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