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Anion, solvent and time dependence of high-spin-low-spin interactions in a 3D coordination polymer

Anion, solvent and time dependence of high-spin-low-spin interactions in a 3D coordination polymer
Anion, solvent and time dependence of high-spin-low-spin interactions in a 3D coordination polymer
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.
1434-1948
3948-3959
Jameson, Guy N.L.
769b56b8-d317-4072-8852-235ae567620c
Werner, Franz
fb9fce65-1444-4d36-9c6f-4bc46efc2dac
Bartel, Matthias
aa24e2f9-6d08-47e6-bd3d-b3f687eca754
Absmeier, Alina
c18835d3-4cd0-4dfe-b5f0-dff163fc600e
Reissner, Michael
dc792c20-ecde-4b3f-9ab1-6d854727d9f3
Kitchen, Jonathan A.
3999f5cb-d53e-4c51-b750-627bd2a1b9b6
Brooker, Sally
2ee9681a-3ff7-41be-88c5-681f66b953ef
Caneschi, Andrea
8a42f893-2193-4839-aefc-fbc71c518958
Carbonera, Chiara
3591a924-d0e8-41bb-bb42-a4d59ef91a97
Létard, Jean-François
9dd850bc-f02c-4aae-ba08-f3651f34b61b
Linert, Wolfgang
538b4d7c-6b28-46ac-a26e-6bad054ffbcf
Jameson, Guy N.L.
769b56b8-d317-4072-8852-235ae567620c
Werner, Franz
fb9fce65-1444-4d36-9c6f-4bc46efc2dac
Bartel, Matthias
aa24e2f9-6d08-47e6-bd3d-b3f687eca754
Absmeier, Alina
c18835d3-4cd0-4dfe-b5f0-dff163fc600e
Reissner, Michael
dc792c20-ecde-4b3f-9ab1-6d854727d9f3
Kitchen, Jonathan A.
3999f5cb-d53e-4c51-b750-627bd2a1b9b6
Brooker, Sally
2ee9681a-3ff7-41be-88c5-681f66b953ef
Caneschi, Andrea
8a42f893-2193-4839-aefc-fbc71c518958
Carbonera, Chiara
3591a924-d0e8-41bb-bb42-a4d59ef91a97
Létard, Jean-François
9dd850bc-f02c-4aae-ba08-f3651f34b61b
Linert, Wolfgang
538b4d7c-6b28-46ac-a26e-6bad054ffbcf

Jameson, Guy N.L., Werner, Franz, Bartel, Matthias, Absmeier, Alina, Reissner, Michael, Kitchen, Jonathan A., Brooker, Sally, Caneschi, Andrea, Carbonera, Chiara, Létard, Jean-François and Linert, Wolfgang (2009) Anion, solvent and time dependence of high-spin-low-spin interactions in a 3D coordination polymer. European Journal of Inorganic Chemistry, 2009 (26), 3948-3959. (doi:10.1002/ejic.200900537).

Record type: Article

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.

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More information

Published date: September 2009
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow, Chemistry, Faculty of Natural and Environmental Sciences

Identifiers

Local EPrints ID: 352496
URI: http://eprints.soton.ac.uk/id/eprint/352496
ISSN: 1434-1948
PURE UUID: e1d1fa3b-13cc-47aa-80ef-7a66a99b871a
ORCID for Jonathan A. Kitchen: ORCID iD orcid.org/0000-0002-7139-5666

Catalogue record

Date deposited: 14 May 2013 14:11
Last modified: 16 Jul 2019 21:33

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