59Co Thermal Sensitivity in Co(III) Trisdithiocarbamate Complexes

IF 4.3 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-03-26 DOI:10.1021/acs.inorgchem.4c05385

Ökten Üngör, Sara Termos, Robert W. Schurko, Joseph M. Zadrozny

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引用次数: 0

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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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.