Journal article
Solvent modified spin crossover in an iron(III) complex: phase changes and an exceptionally wide hysteresis
Wasinee Phonsri, Phimphaka Harding, Lujia Liu, Shane G Telfer, Keith S Murray, Boujemaa Moubaraki, Tamsyn M Ross, Guy NL Jameson, David J Harding
Chemical Science | Royal Society of Chemistry | Published : 2017
DOI: 10.1039/c6sc05317c
Abstract
Solvent effects in a series of Fe(III) spin crossover (SCO) complexes [Fe(qsal-I)2]OTf·sol (sol = MeOH 1, EtOH 2, n-PrOH 3, i-PrOH 4, acetone 5 and MeCN 6) are explored. SCO is abrupt in 1 (following MeOH loss) and 2, gradual for 3 (T1/2 = 199 K) and 4 (T1/2 = 251 K) and incomplete, even up to 350 K, for 5 and 6. In [Fe(qsal-I)2]OTf SCO occurs at T1/2↓ = 225 K and T1/2↑ = 234 K (ΔT = 9 K), while aged samples of 2 exhibit an exceptionally wide hysteresis of 80 K (T1/2↓ = 139 K and T1/2↑ = 219 K). In contrast, fresh samples of 2 exhibit stepped SCO with hysteresis varying from 2 to 42 K. VT-PXRD (variable temperature powder X-ray diffraction) studies indicate a new phase, 2b, is formed upon co..
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Awarded by Thailand Research Fund
Awarded by National Science and Technology Development Agency
Funding Acknowledgements
We thank the Thailand Research Fund (Grant No. RSA5580028 and RSA5880048) and the National Science and Technology Development Agency (Grant No. P-10-11181) for funding this research. KSM thanks the Australian Research Council for a Discovery Project grant to support this work. Parts of this research were undertaken on the MX2 and PD beamlines with the help of Dr Helen Brand and Dr Alan Riboldi-Tunnicliffe from the Australian Synchrotron, Victoria, Australia.