Triggering of Valence Tautomeric Transitions in Dioxolene-Based Cobalt Complexes Influenced by Ligand Substituents, Co-ligands, and Anions

Sundaresan S, Diehl M, Carrella LM, Rentschler E (2022)

Publication Type: Journal article

Publication year: 2022

Journal

Magnetochemistry MDPI publishing

Book Volume: 8

Article Number: 109

Journal Issue: 9

DOI: 10.3390/magnetochemistry8090109

Abstract

We report the multistep synthesis of the 1,1′-(piperazine-1,4-diyl)bis(N,N-bis(pyridin-2-ylmethyl)methanamine)(L^tpbap) octadentate ligand, which, in combination with the known 3,5-di-tert-butylcatechol (3,5-dbcat), allowed the preparation of two di-nuclear cobalt complexes [Co2(L^tpbap)(3,5-dbcat)2](SO4)·5.5MeOH·2H2O (3a) and [Co2(L^tpbap)(3,5-dbcat)2](ClO4)2·1.5H2O (3b). We also report the synthesis of two mono-nuclear cobalt complexes [Co(3,5-dbsq)(3,5-dbcat)(4-Mepip)2] (1) with 4-Mepip being 4-methylpiperidine and (Hpip)[Co(tbcat)2(pip)2]·CH3CN (2) where Hpip denotes a piperidinium cation and tbcat is the tetra-bromocatechol ligand. The obtained complexes were characterized by single-crystal X-ray crystallography, SQUID magnetometry, and IR spectroscopy. The structure of the crystalline material in all the cases was determined at 173 K. The magnetic properties of all complexes were measured between 2 and 380 K. The magnetic data clearly show that mono-nuclear complex 1 and di-nuclear complex 3a exhibit valence tautomerism with onset around 300 K and 370 K, respectively, whereas the other two complexes 2 and 3b remain unchanged over the measured temperature range.

Involved external institutions

Johannes Gutenberg-Universität Mainz (JGU)

Germany (DE)

How to cite

APA:

Sundaresan, S., Diehl, M., Carrella, L.M., & Rentschler, E. (2022). Triggering of Valence Tautomeric Transitions in Dioxolene-Based Cobalt Complexes Influenced by Ligand Substituents, Co-ligands, and Anions. Magnetochemistry, 8(9). https://doi.org/10.3390/magnetochemistry8090109

MLA:

Sundaresan, Sriram, et al. "Triggering of Valence Tautomeric Transitions in Dioxolene-Based Cobalt Complexes Influenced by Ligand Substituents, Co-ligands, and Anions." Magnetochemistry 8.9 (2022).

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