1. EXAFS investigations of temperature-dependent structure in cobalt-59 molecular NMR thermometers
- Author
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Anthony K. Rappé, Anthony J. Campanella, Joseph M. Zadrozny, George E. Sterbinsky, and Tyler M. Ozvat
- Subjects
Aqueous solution ,Materials science ,Extended X-ray absorption fine structure ,010405 organic chemistry ,Chemical shift ,Ethylenediamine ,010402 general chemistry ,01 natural sciences ,Article ,0104 chemical sciences ,Inorganic Chemistry ,chemistry.chemical_compound ,Crystallography ,chemistry ,Yield (chemistry) ,Absorption (chemistry) ,Isotopes of cobalt ,Spectroscopy - Abstract
Cobalt-59 nuclei are known for extremely thermally sensitive chemical shifts (δ), which in the long term could yield novel magnetic resonance thermometers for bioimaging applications. In this manuscript, we apply extended X-ray absorption fine-structure spectroscopy (EXAFS) for the first time to probe the exact variations in physical structure that produce the exceptional thermal sensitivity of the (59)Co NMR chemical shift. We apply the technique to five Co(III) complexes: [Co(NH(3))(6)]Cl(3) (1), [Co(en)(3)]Cl(3) (2) (en = ethylenediamine), [Co(tn)(3)]Cl(3) (3) (tn = trimethylenediamine), [Co(tame)(2)]Cl(3) (4) (tame = 1,1,1-tris(aminomethyl)ethane), and [Co(diNOsar)]Cl(3) (5) (diNOsar = dinitrosarcophagine). The solution-phase EXAFS data reveal increasing Co─N bond distances for these aqueous complexes over a ~50 °C temperature window, expanding by Δr((Co─N)) = 0.0256(6) Å, 0.0020(5) Å, 0.0084(5) Å, 0.0006(5) Å, and 0.0075(6) Å for 1-5, respectively. Computational analyses of the structural changes reveal that increased connectivity between the donor atoms encourages complex structural variations. These results imply that rich temperature-dependent structural variations define the (59)Co NMR thermometry in macrocyclic complexes.
- Published
- 2020