Spin-crossover and high-spin iron(ii) complexes as chemical shift 19F magnetic resonance thermometers

Agnes E. Thorarinsdottir, Alexandra I. Gaudette, T. David Harris*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

61 Scopus citations


The potential utility of paramagnetic transition metal complexes as chemical shift 19F magnetic resonance (MR) thermometers is demonstrated. Further, spin-crossover FeII complexes are shown to provide much higher temperature sensitivity than do the high-spin analogues, owing to the variation of spin state with temperature in the former complexes. This approach is illustrated through a series of FeII complexes supported by symmetrically and asymmetrically substituted 1,4,7-triazacyclononane ligand scaffolds bearing 3-fluoro-2-picolyl derivatives as pendent groups (Lx). Variable-temperature magnetic susceptibility measurements, in conjunction with UV-vis and NMR data, show thermally-induced spin-crossover for [Fe(L1)]2+ in H2O, with T1/2 = 52(1) °C. Conversely, [Fe(L2)]2+ remains high-spin in the temperature range 4-61 °C. Variable-temperature 19F NMR spectra reveal the chemical shifts of the complexes to exhibit a linear temperature dependence, with the two peaks of the spin-crossover complex providing temperature sensitivities of +0.52(1) and +0.45(1) ppm per °C in H2O. These values represent more than two-fold higher sensitivity than that afforded by the high-spin analogue, and ca. 40-fold higher sensitivity than diamagnetic perfluorocarbon-based thermometers. Finally, these complexes exhibit excellent stability in a physiological environment, as evidenced by 19F NMR spectra collected in fetal bovine serum.

Original languageEnglish (US)
Pages (from-to)2448-2456
Number of pages9
JournalChemical Science
Issue number3
StatePublished - 2017

ASJC Scopus subject areas

  • General Chemistry


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