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(4ditz)(3)](2+) [4ditz = 1,4-bis(tetrazol-1-yl) butane I is presented. As seen by X-ray single crystal diffraction, changing the hexafluorophosphate anion in the previously investigated trigonal phase [Fe(4ditz)(3)](PF6)(2) to tetrafluoroborate causes the butylene spacers to adopt three different conformations, whereupon the symmetry is reduced to triclinic (space group Pi). 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/H2O 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.
Anion, Solvent and Time Dependence of High-Spin-Low-Spin Interactions in a 3D Coordination Polymer / GNL.Jameson;F.Werner;M.Bartel;A.Absmeier;M.Reissner;JA.Kitchen;S.Brooker;A.Caneschi;C.Carbonera;JF.Letard;W.Linert. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1434-1948. - STAMPA. - 26:(2009), pp. 3948-3959. [10.1002/ejic.200900537]
Anion, Solvent and Time Dependence of High-Spin-Low-Spin Interactions in a 3D Coordination Polymer
CANESCHI, ANDREA;
2009
Abstract
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(4ditz)(3)](2+) [4ditz = 1,4-bis(tetrazol-1-yl) butane I is presented. As seen by X-ray single crystal diffraction, changing the hexafluorophosphate anion in the previously investigated trigonal phase [Fe(4ditz)(3)](PF6)(2) to tetrafluoroborate causes the butylene spacers to adopt three different conformations, whereupon the symmetry is reduced to triclinic (space group Pi). 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/H2O 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.File | Dimensione | Formato | |
---|---|---|---|
EurJInorgChem_2009.pdf
Accesso chiuso
Descrizione: EurJInorgChem_2009
Tipologia:
Pdf editoriale (Version of record)
Licenza:
Tutti i diritti riservati
Dimensione
693.62 kB
Formato
Adobe PDF
|
693.62 kB | Adobe PDF | Richiedi una copia |
I documenti in FLORE sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.