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59Co Thermal Sensitivity in Co(III) Trisdithiocarbamate Complexes
Ökten Üngör1, Sara Termos2,3, Robert W Schurko2,3
1Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States.
Abstract:
Understanding temperature sensitivity in magnetic resonance is key to novel molecular probes for noninvasive temperature mapping. Herein, we report an investigation of the effects of heavy-donor-atom dithiocarbamate ligands on the variable-temperature 59Co nuclear magnetic resonance (NMR) properties of six Co(III) complexes: Co(et2-dtc)3 (1), Co(bu2-dtc)3 (2), Co(hex2-dtc)3 (3), Co(pyrr-dtc)3 (4), Co(benzyl2-dtc)3 (5) and Co(2,6-dmpip-dtc)3 (6) (et2-dtc = diethyldithiocarbamate; bu2-dtc = dibutyldithiocarbamate; hex2-dtc = dihexyldithiocarbamate; pyrr-dtc = pyrrolidine-dithiocarbamate; benzyl2-dtc = dibenzyldithiocarbamate; and 2,6-dmpip-dtc = 2,6-dimethylpiperidine-dithiocarbamate). This study reveals 59Co chemical-shift temperature dependences of 1.17(3)-1.73(4) ppm/°C as a function of ligand substituents. Solid-state Raman spectroscopic analyses show that more Raman-active Co-S6 vibrational modes correlate to higher thermal sensitivities for these compounds, in line with our current model for temperature sensitivity. Short spin-lattice relaxation T1 times in solution (ca. 200 μs) were observed, and correlation with T2* times and solid-state 59Co NMR analyses reveal that the solution-phase line widths are attributable to quadrupolar relaxation processes, which ultimately lower temperature-sensing resolution.
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