Modification of spin crossover behavior through solvent assisted formation and solvent inclusion in a triply interpenetrating three-dimensional network

Matthias Bartel, Alina Absmeier, Guy N.L. Jameson, Franz Werner, Kenichi Kato, Masaki Takata, Roman Boca, Miki Hasegawa, Kurt Mereiter, Andrea Caneschi, Wolfgang Linert

Research output: Contribution to journalArticlepeer-review

42 Citations (Scopus)

Abstract

The 3D coordination polymer [Fe(4ditz)3](PF6) 2·Solv consists of three interpenetrating infinite networks. There are cavities between iron atoms of different networks, which are partly filled with solvent molecules. With a change of the solvent used during synthesis from methanol to ethanol, the magnetic behavior of the materials changes. Both show an abrupt two-step spin crossover from low spin (S = 0) to high spin (S = 2) with the methanolate curve lying 7 K higher and showing a small hysteresis. Single crystal and powder diffraction studies show that they both have the same structure, but in powder form, the methanolate slowly loses methanol to finally leave about 0.075 MeOH/Fe. In comparison, the bigger ethanol remains at 0.25 EtOH/Fe. These results, in conjunction with thermodynamic data, strongly suggest that the differences in magnetic behavior are largely entropic in nature. Possible reasons for this are discussed.

Original languageEnglish
Pages (from-to)4220-4229
Number of pages10
JournalInorganic chemistry
Volume46
Issue number10
DOIs
Publication statusPublished - 2007 May 14
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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