[Fe(mu-btzmp)2(btzmp)2](ClO4)2: a doubly-bridged 1D spin-transition bistetrazole-based polymer showing thermal hysteresis behaviour

Dalton Trans. 2007 Dec 14:(46):5434-40. doi: 10.1039/b709460d. Epub 2007 Oct 4.

Abstract

The reaction of btzmp (1,2-bis(tetrazol-1-yl)-2-methylpropane) with Fe(ClO4)2 generates a 1D polymeric species, [Fe(mu-btzmp)2(btzmp)2](ClO4)2, showing a steep spin transition (T(1/2) / =136 K and T(1/2) / =133 K) with a 3 K thermal hysteresis. The crystal structure at 100 and 200 K reveals that, in contrast to other bistetrazole based spin-transition systems such as [Fe(endi)3](BF4)2 and [Fe(btzp)3](ClO4)2, the present compound has only two ligands bridging the metallic centres, while the other two coordination positions are occupied by two mono-coordinated (non-bridging) btzmp ligands. This peculiarity confers an unprecedented crystal packing in the series of 1D bistetrazole based polymers. The change in spin state is accompanied by an order/disorder transition of the ClO4* counterion. A careful examination of the structural changes occurring upon the spin transition indicates that this order/disorder is most likely affected by the modification of the [tetrazole-centroid]-ND-Fe angle (which is typical of bistetrazole spin-transition materials). Apart from X-ray analysis, also magnetic susceptibility, Mössbauer and UV-vis spectroscopies have been used to characterise the HS and the LS states of [Fe(mu-btzmp)2(btzmp)2](ClO4)2.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Crystallography, X-Ray
  • Ferric Compounds / chemistry*
  • Magnetics
  • Models, Molecular
  • Perchlorates / chemical synthesis
  • Perchlorates / chemistry
  • Polymers / chemical synthesis
  • Polymers / chemistry
  • Propane / analogs & derivatives*
  • Propane / chemical synthesis
  • Spectrophotometry, Ultraviolet
  • Spectroscopy, Mossbauer
  • Tetrazoles / chemical synthesis
  • Tetrazoles / chemistry*

Substances

  • Ferric Compounds
  • Perchlorates
  • Polymers
  • Tetrazoles
  • Propane