☆ 4.8 Article

Slow Magnetic Relaxation at Zero Field in the Tetrahedral Complex [Co(SPh)4]2-

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2011)

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Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 133, Issue 51, Pages 20732-20734

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/ja2100142

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Categories

Chemistry, Multidisciplinary

Funding

  1. NSF [CHE-1111900]
  2. Tyco Electronics
  3. Direct For Mathematical & Physical Scien [1111900] Funding Source: National Science Foundation
  4. Division Of Chemistry [1111900] Funding Source: National Science Foundation

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The Ph4P+ salt of the tetrahedral complex [Co(SPh)(4)](2-), possessing an S = 3/2 ground state with an axial zero-field splitting of D = -70 cm(-1), displays single-molecule magnet behavior in the absence of an applied magnetic field. At very low temperatures, ac magnetic susceptibility data show the magnetic relaxation time, tau, to be temperature-independent, while above 2.5 K thermally activated Arrhenius behavior is apparent with U-eff 21(1) cm(-1) and tau(0) = 1.0(3) X 10(-7) s. Under an applied field of 1 kOe, tau more closely approximates Arrhenius behavior over the entire temperature range. Upon dilution of the complex within a matrix of the isomorphous compound (Ph4P)(2)[Zn(SPh)(4)], ac susceptibility data reveal the molecular nature of the slow magnetic relaxation and indicate that the quantum tunneling pathway observed at low temperatures is likely mediated by intermolecular dipolar interactions.

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