Structural and magnetic investigations on the CT ion-radical salt (p-(dimethylamino)phenyl)dimethylammoniuin bis(maleonitriledithiolato)nickelate(III)

B. L. Ramakrishna, P. T. Manoharan

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Abstract

A detailed study of (TMPD)Ni(mnt)2 by a variety of physical methods - X-ray crystallography, electronic absorption spectroscopy, magnetic susceptibility, electrical conductivity, and EPR - has been carried out. Though Ni(mnt)2 - and TMPD+ form segregated stacks along the "a" axis in the triclinic modification P1, a number of short contacts between the units facilitate charge transfer from TMPD+ to Ni(mnt)2 -. Both susceptibility and EPR studies indicate two temperature regions, T < 100 K and T > 100 K. In the T < 100 K region, where the behavior is Curie-Weiss type, the decomposition of total susceptibility shows that at 4.2 K about 90% of the contribution comes from the Ni(mnt)2 - stack. A value of exchange (∼120 cm-1) has been found from the dependence of χ on temperature in the T > 100 K region. Powder EPR studies yielded a ratio of De/J to be 1.94 × 10-2. Single-crystal EPR studies at 77 K clearly indicate a change in the principal axis cosines and from line width analysis in the plane perpendicular to "a" give the best fit for J = -6.5 cm-1, De = -0.13 cm-1, and ρ = 5. The line shape analysis shows low-dimensional behavior for B∥a and nearly Lorentzian behavior for B⊥a.

Original languageEnglish (US)
Pages (from-to)2113-2123
Number of pages11
JournalInorganic Chemistry
Volume22
Issue number15
StatePublished - 1983
Externally publishedYes

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Paramagnetic resonance
Salts
Ions
salts
magnetic permeability
ions
crystallography
line shape
X ray crystallography
absorption spectroscopy
Magnetic susceptibility
Absorption spectroscopy
charge transfer
Linewidth
Powders
decomposition
Charge transfer
electrical resistivity
temperature
single crystals

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Structural and magnetic investigations on the CT ion-radical salt (p-(dimethylamino)phenyl)dimethylammoniuin bis(maleonitriledithiolato)nickelate(III). / Ramakrishna, B. L.; Manoharan, P. T.

In: Inorganic Chemistry, Vol. 22, No. 15, 1983, p. 2113-2123.

Research output: Contribution to journalArticle

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AB - A detailed study of (TMPD)Ni(mnt)2 by a variety of physical methods - X-ray crystallography, electronic absorption spectroscopy, magnetic susceptibility, electrical conductivity, and EPR - has been carried out. Though Ni(mnt)2 - and TMPD+ form segregated stacks along the "a" axis in the triclinic modification P1, a number of short contacts between the units facilitate charge transfer from TMPD+ to Ni(mnt)2 -. Both susceptibility and EPR studies indicate two temperature regions, T < 100 K and T > 100 K. In the T < 100 K region, where the behavior is Curie-Weiss type, the decomposition of total susceptibility shows that at 4.2 K about 90% of the contribution comes from the Ni(mnt)2 - stack. A value of exchange (∼120 cm-1) has been found from the dependence of χ on temperature in the T > 100 K region. Powder EPR studies yielded a ratio of De/J to be 1.94 × 10-2. Single-crystal EPR studies at 77 K clearly indicate a change in the principal axis cosines and from line width analysis in the plane perpendicular to "a" give the best fit for J = -6.5 cm-1, De = -0.13 cm-1, and ρ = 5. The line shape analysis shows low-dimensional behavior for B∥a and nearly Lorentzian behavior for B⊥a.

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