Journal article

Valence tautomerism and spin crossover in pyridinophane-cobalt-dioxolene complexes: an experimental and computational study

Tina Tezgerevska, Elodie Rousset, Robert W Gable, Guy NL Jameson, E Carolina Sanudo, Alyona Starikova, Colette Boskovic

Dalton Transactions | ROYAL SOC CHEMISTRY | Published : 2019


Compounds [Co(L-N4R2)(dbdiox)](BPh4) (L-N4R2 = N,N'-di-alkyl-2,11-diaza[3.3]-(2,6)pyridinophane, R = iPr (1a), Et (2a); dbdiox = 3,5-di-tert-butyldioxolene) and [M(L-N4iPr2)(dbdiox)](BPh4) (M = Mn (3a), Fe (4a)) have been synthesized and investigated with a view to possible valence tautomeric (VT) or spin crossover (SCO) interconversions. Single crystal X-ray diffraction data for all compounds at 100 or 130 K indicate trivalent metal cations and di-tert-butylcatecholate (dbcat2-) dioxolene ligands. Variable temperature magnetic susceptibility data for all species between 2 and 340 K are consistent with these redox states, with low spin configurations for the cobalt(iii) ions and high spin fo..

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Awarded by Australian Research Council

Awarded by Spanish Government

Awarded by Ministry of Science and Higher Education of the Russian Federation

Funding Acknowledgements

CB thanks the Australian Research Council for financial support (DP150100353). ECS acknowledges financial support from the Spanish Government, (Grant CTQ2015-68370-P). AS thanks the Ministry of Science and Higher Education of the Russian Federation (State assignment no. 4.1774.2017/4.6). Part of this research was undertaken on the MX1 beamline at the Australian Synchrotron, Victoria, Australia. Thanks to Dr Roger Mulder for his assistance with collecting the variable temperature NMR data.