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Synthesis, characterization, and electrochemistry of SNS cobalt(II) tridentate complexes

Abstract

The preparation of two cobalt(II) complexes that contain a tridentate ligand with sulfur, nitrogen, and sulfur donor atoms is described. The tridentate ligand precursors are based on bis-imidazole or bis-triazole moieties. The complex based on a bis-imidazole precursor was green in color and was prepared in 93.3% yield. The complex based on a bis-triazole precursor was blue-green in color and was prepared in 69.8% yield. Single-crystal structures of both complexes were obtained. Both complexes contain [BF4] as the counter-anion. Based on the single-crystal structure, the molecular geometry around the cobalt(II) center is distorted tetrahedral. EPR spectra were obtained for both complexes at 4 K. Each complex has axial symmetry for its electron density and each cobalt(II) complex has S = 3/2. For the complex based on a bis-imidazole precursor, the UV–Vis peaks were observed at 696 nm, 629 nm, 585 (sh) nm, and 375 (sh) nm. For the complex based on bis-triazole, UV–Vis peaks were observed at 681, 613, 570, 243, 239, 236, 233, 230, 227, and 210 nm. Cyclic voltammetry spectra were obtained for both complexes. Both the ligand precursor and the cobalt(II) complexes are redox active. All of the redox waves were irreversible.

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Data availability

The data are stored on Dropbox and on computers at Fairfield University. The CIF files have been deposited with the Cambridge Structure Database.

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Acknowledgements

JRM acknowledges the National Science Foundation Major Research Instrumentation Program for the purchases of an EPR spectrometer (CHE-08539), X-ray diffractometer (CHE-1039027), and a 400 MHz NMR Spectrometer (CHE-1827854). JRM is grateful for receiving generous support from the NASA CT Space Grant (Award number P-1168) in support of this work. EMA, RMK, SCB, SEZ, and EEM received Hardiman Research Scholarships when working on this project at Fairfield University. ACW and SCB are supported by NIH award (R01-GM110390).

Funding

John Miecznikowski has received funding from the National Science Foundation (CHE-08539 and CHE-1827854), NASA Connecticut Space Grant (P-1168), and Fairfield University in support of this work. John Miecznikowski is employed by Fairfield University and has a visiting appointment in the Department of Chemistry at Yale University. John Miecznikowski has served on review panels at the National Science Foundation. Jerry Jasinski has received funding from the National Science Foundation (CHE-1039027) which supported this work. Jerry Jasinski was employed by Keene State College when the work was performed. Samantha Zygmont, Sheila Bonitatibus, Emilse Almanza, Rami Kharbouch, and Emma Mircovich were supported by Fairfield University (Hardiman Scholarship) when the work was performed. Eric Reinheimer and Pierre LeMageres are employed by Rigaku Corporation Americas. Andrew Weitz is a post-doctoral fellow at Boston University and is supported by a grant from the NIH (R01-GM110390). Sheila Bonitatibus is also supported by (R01-GM110390).

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Contributions

JM contributed to conceptualization, writing original draft, writing review and editing, visualization, supervision, project administration, and funding acquisition; SZ and SB contributed to investigation, validation, visualization, and writing original draft; JPJ and MK contributed to investigation; EA, RK, and EM contributed to investigation and validation; PLM and ER contributed to investigation and visualization; AW contributed to investigation, visualization, and revising draft.

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Correspondence to John R. Miecznikowski.

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This article is dedicated to Professor Jerry P. Jasinski, a great collaborator and friend.

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Miecznikowski, J.R., Zygmont, S.E., Jasinski, J.P. et al. Synthesis, characterization, and electrochemistry of SNS cobalt(II) tridentate complexes. Transit Met Chem 47, 127–137 (2022). https://doi.org/10.1007/s11243-022-00496-6

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