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Anion, Solvent and Time Dependence of High‐Spin–Low‐Spin Interactions in a 3D Coordination Polymer
Author(s) -
Jameson Guy N. L.,
Werner Franz,
Bartel Matthias,
Absmeier Alina,
Reissner Michael,
Kitchen Jonathan A.,
Brooker Sally,
Caneschi Andrea,
Carbonera Chiara,
Létard JeanFrançois,
Linert Wolfgang
Publication year - 2009
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200900537
Subject(s) - chemistry , spin crossover , crystallography , spin transition , triclinic crystal system , spin states , hexafluorophosphate , solvent , counterion , ion , crystal structure , inorganic chemistry , ionic liquid , organic chemistry , catalysis
A thorough investigation into the role of the counterion and occluded solvent on the structure and spin‐crossover behaviour of the threefold interpenetrated network [Fe(4 ditz ) 3 ] 2+ [4 ditz = 1,4‐bis(tetrazol‐1‐yl)butane] is presented. As seen by X‐ray single crystal diffraction, changing the hexafluorophosphate anion in the previously investigated trigonal phase [Fe(4 ditz ) 3 ](PF 6 ) 2 to tetrafluoroborate causes the butylene spacers to adopt three different conformations, whereupon the symmetry is reduced to triclinic (space group P $\bar {1}$ ). X‐ray powder diffraction and NMR spectroscopy provide evidence for the incorporation of statistically distributed ethanol molecules in the cavities of the compound, whose amount depends on whether absolute ethanol or a binary system, ethanol/water (95:5, v/v), is used as solvent. The phase precipitated from EtOH/H 2 O features a metastable high‐spin (HS) state when rapidly cooled, a sharp spin transition to a mixed HS/LS (1:1) state at around 90 K on slow cooling with an approximately 10 K hysteresis and LIESST appears, whereas the sample synthesised from absolute ethanol shows a more gradual spin transition at the same temperature without hysteresis.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)