Reversible quantitative guest sensing via spin crossover of an iron(ii) triazole.
نویسندگان
چکیده
A new phenyl-triazole-pyrazine ligand, 4-p-tolyl-3-(phenyl)-5-(2-pyrazinyl)-1,2,4-triazole (tolpzph), was prepared in order to enforce pyrazine coordination of the iron(ii) centre in the resulting complex, [FeII(tolpzph)2(NCS)2]·THF (1·THF). Structure determinations carried out on this discrete mononuclear complex, 1·THF, at 273 K (mostly high spin) and 100 K (mostly low spin) demonstrate this was successful, and that spin crossover (SCO) occurred on cooling. Subsequent magnetic measurements on 1·THF revealed that it shows highly sensitive and reversible solvent-dependent SCO, with T1/2(1·THF) = 255 K vs. T1/2(1) = 212 K (with SCO of 1 more abrupt and occurring with a 4 K hysteresis loop), a drop of 43 K due to THF loss. This is reversible over at least 10 cycles of re-solvating with THF followed by re-drying, so 1 ↔ 1·THF can be considered an 'on-off' THF sensor, monitored by the T1/2 reversibly shifting (by 43 K). Furthermore, quantitative sensing of the fractional amount of THF present in 1·nTHF, 0 ≤ n ≤ 1, is demonstrated. Monitoring the T1/2 and using TGA to quantify n(THF) revealed a linear dependence (25 data points; Pearson r2 = 0.93): T1/2 = 41.1n(THF) + 219. Finally, 1 is also shown to take up CHCl3 [T1/2(1·CHCl3) = 248 K], with a logarithmic T1/2 dependence on the fractional amount of CHCl3 present (10 data points; Pearson r2 = 0.98): T1/2 = 27.0 log10[n(CHCl3)] + 243. This study is a proof of principle that a (multi-use) quantitative sensor material based on spin crossover is feasible.
منابع مشابه
Reversible quantitative guest sensing via spin crossover of an iron(ii) triazole† †Electronic supplementary information (ESI) available: Synthetic details, NMR spectra, instrumentation, plus additional structural, magnetic and TGA information and diagrams. CCDC 1434103 and 1434104. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc04583e Click here for additional data file. Click here for additional data file.
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عنوان ژورنال:
- Chemical science
دوره 7 4 شماره
صفحات -
تاریخ انتشار 2016