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

Suzanne M. Neville; Gregory J. Halder; Karena W. Chapman; Martin B. Duriska; Peter D. Southon; John D. Cashion; Jean François Létard; Boujemaa Moubaraki; Keith S. Murray; Cameron J. Kepert

doi:10.1021/ja077958f

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

Suzanne M. Neville
, Gregory J. Halder
, Karena W. Chapman
, Martin B. Duriska
, Peter D. Southon
, John D. Cashion
, Jean François Létard
, Boujemaa Moubaraki
, Keith S. Murray
, Cameron J. Kepert

Chemistry

The University of Sydney
Monash University
Argonne National Laboratory
Institut de Chimie de la Matière Condensée de Bordeaux

Research output: Contribution to journal › Article › peer-review

225 Scopus citations

Abstract

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 (/4/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.

Original language	English
Pages (from-to)	2869-2876
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	130
Issue number	9
DOIs	https://doi.org/10.1021/ja077958f
State	Published - Mar 5 2008

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Neville, S. M., Halder, G. J., Chapman, K. W., Duriska, M. B., Southon, P. D., Cashion, J. D., Létard, J. F., Moubaraki, B., Murray, K. S., & Kepert, C. J. (2008). Single-crystal to single-crystal structural transformation and photomagnetic properties of a porous iron(II) spin-crossover framework. Journal of the American Chemical Society, 130(9), 2869-2876. https://doi.org/10.1021/ja077958f

@article{24148de93bc04f4797e9985d170bc88d,

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

abstract = "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 (/4/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.",

author = "Neville, \{Suzanne M.\} and Halder, \{Gregory J.\} and Chapman, \{Karena W.\} and Duriska, \{Martin B.\} and Southon, \{Peter D.\} and Cashion, \{John D.\} and L{\'e}tard, \{Jean Fran{\c c}ois\} and Boujemaa Moubaraki and Murray, \{Keith S.\} and Kepert, \{Cameron J.\}",

year = "2008",

month = mar,

day = "5",

doi = "10.1021/ja077958f",

language = "English",

volume = "130",

pages = "2869--2876",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

number = "9",

}

Neville, SM, Halder, GJ, Chapman, KW, Duriska, MB, Southon, PD, Cashion, JD, Létard, JF, Moubaraki, B, Murray, KS & Kepert, CJ 2008, 'Single-crystal to single-crystal structural transformation and photomagnetic properties of a porous iron(II) spin-crossover framework', Journal of the American Chemical Society, vol. 130, no. 9, pp. 2869-2876. https://doi.org/10.1021/ja077958f

TY - JOUR

T1 - Single-crystal to single-crystal structural transformation and photomagnetic properties of a porous iron(II) spin-crossover framework

AU - Neville, Suzanne M.

AU - Halder, Gregory J.

AU - Chapman, Karena W.

AU - Duriska, Martin B.

AU - Southon, Peter D.

AU - Cashion, John D.

AU - Létard, Jean François

AU - Moubaraki, Boujemaa

AU - Murray, Keith S.

AU - Kepert, Cameron J.

PY - 2008/3/5

Y1 - 2008/3/5

N2 - 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 (/4/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.

AB - 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 (/4/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.

UR - https://www.scopus.com/pages/publications/40949111877

U2 - 10.1021/ja077958f

DO - 10.1021/ja077958f

M3 - Article

AN - SCOPUS:40949111877

SN - 0002-7863

VL - 130

SP - 2869

EP - 2876

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 9

ER -

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

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