American Chemical Society
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Synthesis of Nanocrystals and Particle Size Effects Studies on the Thermally Induced Spin Transition of the Model Spin Crossover Compound [Fe(phen)2(NCS)2]

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journal contribution
posted on 2015-08-17, 00:00 authored by Francisco Javier Valverde-Muñoz, Ana B. Gaspar, Sergii I. Shylin, Vadim Ksenofontov, José A. Real
Surfactant-free nanocrystals of the model spin-crossover compound [Fe­(phen)2(NCS)2] (phen: 1,10-phenanthroline) have been synthesized applying the reverse micelle technique. The morphology of the nanocrystals, characterized by scanning electronic microscopy, corresponds to rhombohedric platelets with dimensions ranging from 203 × 203 × 106 nm to 142 × 142 × 74 nm. Variation of the concentration of the Fe­(BF4)2·6H2O salt in the synthesis has been found to have little influence on the crystallite size. In contrast, the solvent–surfactant ratio (ω) is critical for a good particle growth. The spin transition of the nanocrystals has been characterized by magnetic susceptibility measurements and Mössbauer spectroscopy. The nanocrystals undergo an abrupt and more cooperative spin transition in comparison with the bulk compound. The spin transition is centered in the interval of temperature of 175–185 K and is accompanied by 8 K of thermal hysteresis width. The crystallite quality more than the crystallite size is responsible for the higher cooperativity. The magnetic properties of the nanocrystals embedded in organic polymers such as polyethylene glycol, nujol, glycerol, and triton have been studied as well. The spin transition in the nanocrystals is affected by the polymer coating. The abrupt and first-order spin transition transforms into a more continuous spin transition as a result of the chemical pressure asserted by the organic polymers on the Fe­(II) centers.