Tuning the Spin-Crossover Behaviour in Fe(II) Polymeric Composites for Food Packaging Applications

Although the spin-crossover (SCO) phenomenon is well documented, tuning the SCO behaviour remains a challenging task. This could be mainly attributed to the 'delicate' nature of the phenomenon; cooperativity expressed through differences in particle size and morphologies, and electrostatic interactions could significantly affect the process. The goal of the present effort is dual bearing both scientific and technological interest. Firstly, to examine the technological potential of SCO complexes by incorporating them into polymers, and secondly-and most importantly-to investigate if polymer-SCO complex interactions could occur and could affect the SCO behaviour, depending on the structural properties of both the polymer matrix and the SCO complex. In this context, two different polymers, polylactic acid (PLA) and polysulphone (PSF), which are capable of developing different interactions with the inclusions, and the SCO complexes [Fe(abpt)(2){N(CN)(2)}(2)] and [Fe(abpt)(2)(SCN)(2)] were examined; abpt is the N,N'-bidentate chelating ligand 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole. The composites were characterised through scanning electron microscopy (SEM), attenuated total reflectance infrared (ATR/FTIR), and Raman spectroscopy. In addition, the potential migration release of the SCO compounds from the polymeric matrices and their toxicity evaluation were also studied. In addition, the potential migration release of the SCO compounds from the polymeric matrices was evaluated, and their insignificant toxicity was also verified. Temperature-dependent Raman spectra were collected in situ for the monitoring of the SCO behaviour after the incorporation of the Fe(II) complexes into the polymers; an upshift of the T-1/2 transition and a hysteretic behaviour was detected for PSF-SCO composites, compared with the non-hysteretic behaviour of the pristine SCO complexes.