SCIORTINO, Natasha F.; NEVILLE, Suzanne M.; DESPLANCHES, Cédric; LÉTARD, Jean-François; MARTINEZ, Victor; REAL, José Antonio; MOUBARAKI, Boujemaa; MURRAY, Keith S.; KEPERT, Cameron J.

doi:10.1002/chem.201400367

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SCIORTINO, Natasha F.
School of Chemistry

NEVILLE, Suzanne M.
School of Chemistry

DESPLANCHES, Cédric
Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB]

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Chemistry - A European Journal. 2014, vol. 20, n° 24, p. 7448-7457

Wiley-VCH Verlag

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Two new isostructural iron(II) spin-crossover (SCO) framework (SCOF) materials of the type [Fe(dpms)2 (NCX)2 ] (dpms=4,4'-dipyridylmethyl sulfide; X=S (SCOF-6(S)), X=Se (SCOF-6(Se))) have been synthesized. The 2D framework materials consist of undulating and interpenetrated rhomboid (4,4) nets. SCOF-6(S) displays an incomplete SCO transition with only approximately 30 % conversion of high-spin (HS) to low-spin iron(II) sites over the temperature range 300-4 K (T1/2 =75 K). In contrast, the NCSe(-) analogue, SCOF-6(Se), displays a complete SCO transition (T1/2 =135 K). Photomagnetic characterizations reveal quantitative light- induced excited spin-state trapping (LIESST) of metastable HS iron(II) sites at 10 K. The temperature at which the photoinduced stored information is erased is 58 and 50 K for SCOF-6(S) and SCOF-6(Se), respectively. Variable-pressure magnetic measurements were performed on SCOF-6(S), revealing that with increasing pressure both the T1/2 value and the extent of spin conversion are increased; with pressures exceeding 5.2 kbar a complete thermal transition is achieved. This study confirms that kinetic trapping effects are responsible for hindering a complete thermally induced spin transition in SCOF-6(S) at ambient pressure due to an interplay between close T1/2 and T(LIESST) values.< Réduire

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Chalcogens

Coordination polymers

Iron

Magnetic properties

Spin crossover

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An investigation of photo- and pressure-induced effects in a pair of isostructural two-dimensional spin-crossover framework materials

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