Influence of ligand encapsulation on cobalt-59 chemical-shift thermometry

Chemical Science
Tyler M OzvatJoseph M Zadrozny

Abstract

Thermometry via magnetic resonance imaging (MRI) would provide a powerful noninvasive window into physiological temperature management. Cobalt-59 nuclear spins demonstrate exceptional temperature dependence of their NMR chemical shifts, yet the insight to control this dependence via molecular design is lacking. We present the first systematic evidence that encapsulation of this spin system amplifies the temperature sensitivity. We tested the temperature dependence of the 59Co chemical shift (Δδ/ΔT) in a series of five low-spin cobalt(iii) complexes as a function of increasing encapsulation within the 1st coordination sphere. This study spans from [Co(NH3)6]Cl3, with no interligand connectivity, to a fully encapsulated dinitrosarcophagine (diNOsar) complex, [Co(diNOsar)]Cl3. We discovered Δδ/ΔT values that span from 1.44(2) ppm °C-1 in [Co(NH3)6]Cl3 to 2.04(2) ppm °C-1 in [Co(diNOsar)]Cl3, the latter among the highest for a molecular complex. The data herein suggest that designing 59Co NMR thermometers toward high chemical stability can be coincident with high Δδ/ΔT. To better understand this phenomenon, variable-temperature UV-Vis, 59Co NMR relaxation, Raman spectroscopic, and variable-solvent investigations were performed. Dat...Continue Reading

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Citations

Mar 21, 2020·Physical Chemistry Chemical Physics : PCCP·Andrej Antušek, Michal Repisky
Jun 2, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Tyler M OzvatJoseph M Zadrozny
Jun 8, 2021·Magnetochemistry·Tyler M OzvatJoseph M Zadrozny

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Methods Mentioned

BETA
NMR
electron paramagnetic resonance

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