NEVILLE, Suzanne M.; HALDER, Gregory J.; CHAPMAN, Karena W.; DURISKA, Martin B.; SOUTHON, Peter D.; CASHION, John D.; LÉTARD, Jean-François; MOUBARAKI, Boujemaa; MURRAY, Keith S.; KEPERT, Cameron J.

doi:10.1021/ja077958f

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NEVILLE, Suzanne M.
School of Chemistry
School of Chemistry

HALDER, Gregory J.
School of Chemistry
Material Science Division [ANL] [MSD]

CHAPMAN, Karena W.
X-ray Science Division [XSD]

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Journal of the American Chemical Society. 2008, vol. 130, n° 9, p. 2869-2876

American Chemical Society

Résumé en anglais

The porous coordination framework material, Fe(NCS)2(bped)2·3EtOH, SCOF-3(Et) (where bped is DL-1,2-bis(4'-pyridyl)-1,2-ethanediol), displays a spin-crossover (SCO) transition that has been stimulated both thermally and by light irradiation. The one-step thermal SCO (70-180 K) is sensitive to the presence of molecular guests, with a more gradual transition (70-225 K) apparent following the desorption of ethanol molecules that hydrogen bond to the spin centers. Additional intraframework hydrogen-bonding interactions stabilize the vacant one-dimensional pore structure of the apohost, SCOF-3, despite a dramatic single-crystal to single-crystal (SC-SC) structural change upon removal of the guests. Comprehensive structural analyses throughout this transformation, from primitive orthorhombic (Pccn) to body-centered tetragonal (I4/mcm), reveal a flexing of the framework and a dilation of the channels, with an accompanying subtle distortion of the iron(II) coordination geometry. Photomagnetic measurements of the light-induced excited spin state trapping (LIESST) effect have been used to assess the degree of cooperativity in this system.< Réduire

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Spin crossover

Single crystal

Flexible framework

Porous framework

Iron(II)

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Single-crystal to single-crystal structural transformation and photomagnetic properties of a porous iron(II) spin-crossover framework

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