EXAFS investigations of temperature-dependent structure in cobalt-59 molecular NMR thermometers

Ozvat, Tyler M.; Sterbinsky, George E.; Campanella, Anthony J.; Rappé, Anthony K.; Zadrozny, Joseph M.

doi:10.1039/d0dt01391a

Title: EXAFS investigations of temperature-dependent structure in cobalt-59 molecular NMR thermometers

Journal Article · 31 December 2019 · Dalton Transactions

DOI: https://doi.org/10.1039/d0dt01391a · OSTI ID:1776839

^[1]; Sterbinsky, George E. ^[2]; Campanella, Anthony J. ^[1];

^[1];

^[1]

Colorado State Univ., Fort Collins, CO (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

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 (EXAFS) spectroscopy for the first time to probe the exact variations in physical structure that produce the exceptional thermal sensitivity of the ⁵⁹Co NMR chemical shift. We apply this spectroscopic technique to five Co(III) complexes: [Co(NH3)6]Cl3 (1), [Co(en)₃]Cl₃ (2) (en = ethylenediamine), [Co(tn)₃]Cl₃ (3) (tn = trimethylenediamine), [Co(tame)₂]Cl₃ (4) (tame = 1,1,1-tris(aminomethyl)ethane), and [Co(diNOsar)]Cl₃ (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. Finally, these results imply that rich temperature-dependent structural variations define ⁵⁹Co NMR thermometry in macrocyclic complexes.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Institutes of Health (NIH); National Science Foundation (NSF); USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1776839

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 45 Vol. 49; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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