In:
Dalton Transactions, Royal Society of Chemistry (RSC), Vol. 51, No. 44 ( 2022), p. 16876-16889
Abstract:
Synthesis and magnetic characterization of a family of cobalt-dioxolene complexes [(Me 2 TPA)Co(36-DBCat)] (1), [(Me 2 TPA)Co(36-DBCat)](PF 6 ) (2) and [(Me 2 TPA)Co(diox-(OMe) 3 )](BPh 4 ) (3) (Me 2 TPA = bis(6-methyl-2-pyridyl)methyl-(2-pyridylmethyl)amine; 36-DBCat = dianion of 3,6-di- tert -butylcatechol; diox-(OMe) 3 – 2,5-di- tert -butyl-3,3,4-trimethoxy-6-oxocyclohexa-1,4-dienolate) is reported. The neutral complex 1 is found to form hexa- (CoO 2 N 4 , 1a) and pentacoordinated (CoO 2 N 3 , 1b) isomers. Variable temperature single crystal X-ray diffraction analysis of 1a and 1b clearly indicates the presence of the high-spin divalent metal ion and the dianionic catecholate form of the dioxolene ligand. Oxidation of 1 by ferrocenium hexafluorophosphate results in the formation of the ionic octahedral complex 2, demonstrating thermally induced valence-tautomeric transition (ls-Co III -36-DBCat ⇄ hs-Co II -36-DBSQ) in the solid state with T 1/2 = 175 K (36-DBSQ = radical-anionic semiquinonate form of the redox-ligand). In contrast, aerial oxidation of 1 is accompanied by changes in the structure of dioxolene resulting in oxocyclohexadienolate ligand and the formation of an ionic complex of high-spin divalent cobalt (3). Compounds 1a, 1b, and 3 are found to demonstrate a field-induced single-ion magnet behavior. The analysis of the electronic structures of 1, 2 and 3 with the aid of DFT and SA-CASSCF/NEVPT2 calculations is also given.
Type of Medium:
Online Resource
ISSN:
1477-9226
,
1477-9234
Language:
English
Publisher:
Royal Society of Chemistry (RSC)
Publication Date:
2022
detail.hit.zdb_id:
1472887-4
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