Structural and Magnetic Investigations on the CT Ion-Radical Salt (p-(Dimethylamino)phenyl)dimethylammonium Bis(maleonitriledithiolato)nickelate(III)

B. L. Ramakrishna, P. T. Manoharan

Research output: Contribution to journalArticle

31 Scopus citations

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 Dc 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 p = 5. The line shape analysis shows low-dimensional behavior for B\\a and nearly Lorentzian behavior for Ba.

Original languageEnglish (US)
Pages (from-to)2113-2123
Number of pages11
JournalInorganic chemistry
Volume22
Issue number15
DOIs
StatePublished - Jul 1983

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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