4.8 Article

Bistability of Magnetization without Spin-Transition in a High-Spin Cobalt(II) Complex due to Angular Momentum Quenching

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 131, Issue 13, Pages 4560-+

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/ja808448j

Keywords

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Funding

  1. Japan Society for the Promotion of Science [18350088, 18066013, 18GS0207]
  2. Ministry of Culture, Sports, Science, and Technology of Japan (MEXT)
  3. CREST of the Japan Science and Technology Cooperation
  4. Grants-in-Aid for Scientific Research [18066013, 18350088] Funding Source: KAKEN

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[Co(NO3)(2)L] (L: 2,6-di(pyrazol-1-yl)pyrazine) (1) exhibits an abrupt transition with hysteresis in magnetic susceptibility between 228 and 240 K. The results of spectroscopic and XRD measurements showed that I is in the high spin state in the whole temperature range. Therefore the observed hysteresis is not due to a spin transition but corresponds to a partial quenching of the angular momentum contribution to the magnetic susceptibility. Crystallographic measurements on the low- and high-temperature form of 1, combined with DFT calculations, showed that a symmetric twisting of the coordinating nitrate ions upon the transition is the most important factor in the orbital quenching mechanism. Utilizing such quenching to control magnetic properties can be a new approach to engineer transition metal complexes with magnetic functionalities without changing their spin or oxidation state.

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