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Tuning the spin-crossover temperature of polynuclear iron(II)–triazole complexes in solution by water and preparation of thermochromic fibers

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Abstract

The spin-crossover temperatures of alkyl-substituted Fe2+–triazole complexes with the counter ions 4-dodecylbenzenesulfonate (DBS−) and 2-naphthalenesulfonate (2ns−) are strongly influenced by water in the dissolved state, whereby the low-spin state is stabilized by water. This effect was found to be more pronounced in complexes with the counter ion DBS− compared to 2ns−. It appears that non-coordinating water molecules interact with the counter ion and thus alter the ligand-field splitting. Notably, the spin-crossover temperature depends only on the Fe2+/H2O ratio and not on the concentration of the complex in solution. As a consequence, the spin-crossover temperature can be controlled by the Fe2+/H2O ratio (for DBS− complexes within a temperature range of 7–47 °C), and on the other hand small amounts of water (in the ppm range) can be detected in apolar solvents. Furthermore, fibers of blends of the complex [Fe(C18trz)3](DBS)2 with ultra-high molecular weight polyethylene (UHMWPE) could be prepared. In these fibers, spin-crossover is maintained leading to pronounced thermochromism as in the bulk material, indicating essentially no interaction between UHMWPE and Fe2+–triazole complex.

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Acknowledgements

We thankfully acknowledge Dr. Martin Willeke for valuable advice regarding this study and for providing access to a temperature-controllable UV/Vis spectrometer. Furthermore, we thank the Swiss National Science Foundation (No. 200021_137550) for financial support and the COST Action CM1302 “European Network on Smart Inorganic Polymers (SIPs)” as a platform for inspiration.

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  1. Department of Materials, Eidgenössische Technische Hochschule (ETH) Zürich, Vladimir-Prelog-Weg 5, 8093, Zurich, Switzerland

    Irene Bräunlich, Samuel Lienemann, Christiane Mair, Paul Smith & Walter Caseri

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  1. Irene Bräunlich
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  2. Samuel Lienemann
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  3. Christiane Mair
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  5. Walter Caseri
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Correspondence to Walter Caseri.

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Bräunlich, I., Lienemann, S., Mair, C. et al. Tuning the spin-crossover temperature of polynuclear iron(II)–triazole complexes in solution by water and preparation of thermochromic fibers. J Mater Sci 50, 2355–2364 (2015). https://doi.org/10.1007/s10853-014-8704-3

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