5-Aryl-2-(3,5-dialkyl-4-hydroxyphenyl)-4,4-dimethyl-4H-imidazole 3-Oxides and Their Redox Species: How Antioxidant Activity of 1-Hydroxy-2,5-dihydro-1H-imidazoles Correlates with the Stability of Hybrid Phenoxyl-Nitroxides.

Cyclic nitrones of the imidazole series, containing a sterically hindered phenol group, are promising objects for studying antioxidant activity; on the other hand, they can form persistent hybrid phenoxyl-nitroxyl radicals (HPNs) upon oxidation. Here, a series of 5-aryl-4,4-dimethyl-4H-imidazole 3-oxides was obtained by condensation of aromatic 2-hydroxylaminoketones with 4-formyl-2,6-dialkylphenols followed by oxidation of the initially formed N-hydroxy derivatives. It was shown that the antioxidant activity of both 1-hydroxy-2,5-dihydroimidazoles and 4H-imidazole 3-oxides increases with a decrease in steric volume of the alkyl substituent in the phenol group, while the stability of the corresponding HPNs generated from 4H-imidazole 3-oxides reveals the opposite tendency.

Magnetic Properties of π-Conjugated Hybrid Phenoxyl-Nitroxide Radicals with Extended π-Spin Delocalization.

A series of stable and genuinely organic open-shell systems, π-conjugated phenoxyl-nitroxide free radicals (hybrid phenoxyl-nitroxide radicals), have been synthesized and their magnetic properties in the crystalline state investigated, revealing their usefulness as new building blocks for molecular magnetic materials. The salient electronic structure of the hybrid phenoxyl-nitroxide radicals is extended π-spin delocalization from the nitroxide moiety, mediating the localization effect intrinsic to nitroxide radicals. Five representative hybrid radicals containing an aliphatic, aromatic, and heteroaromatic substituent in the side part of the compact hybrid radical centers were synthesized, and their molecular/crystal structures in the crystalline state were determined by X-ray diffraction analyses. CW X-band ESR, 1H-ENDOR spectroscopy, and DFT calculations for the hybrid radicals confirmed that an unpaired spin delocalizes over the whole molecular frame including the nonconjugated fragments, suggesting the possibility of tuning their electronic properties through substituent effects in the crystalline state. Significant influence of the phenoxyl moiety on the electronic structure was analyzed in terms of the g-tensor calculations. The SQUID magnetization measurements revealed that the nitroxides bearing alkyl or aromatic substituents behave as 3D Curie-Weiss paramagnets with weak antiferromagnetic (AFM) (Θ = -1 to -2.6 K) or ferromagnetic (FM) (Θ = +0.33 K) spin-spin exchange interactions. On the other hand, heteroaromatically substituted hybrid phenoxyl-nitroxide showed significant AFM interactions with J/kB = -25.6 K. The analysis of the bulk magnetic properties based on the crystallographic data and DFT calculations revealed competition between the intermolecular AFM and FM interactions which originate from the C-O(phenoxyl)···Me(nitroxide) or (N)O-C(arom) infinite 1D head-to-tail chains and the C(arom)-C(arom) head-over-tail dimers forming 3D networks in their crystal lattices.

The Suzuki-Miyaura reaction as a tool for modification of phenoxyl-nitroxyl radicals of the 4H-imidazole N-oxide series.

2-(3,5-Di-tert-butyl-4-hydroxyphenyl)-5-(4-iodophenyl)-4,4-dimethyl-4H-imidazole 3-oxide reacts with phenylboronic acid and its substituted derivatives in a cross-coupling reaction of the Suzuki-Miyaura type to form 5-biphenyl derivatives of 4H-imidazole-N-oxide. Interaction of the same compound with B2(pin)2 in the presence of PdCl2(PPh3)2 proceeds through the formation of intermediate 1,3,2-dioxoborolane and leads to the product of homocoupling: biphenyl-bis(imidazole). Oxidation of the resultant imidazoles with lead dioxide quantitatively yields stable conjugated phenoxyl-nitroxyl mono- and diradicals, which are of interest as electroactive paramagnetic materials. The crystal structure of the monoradical, 2,6-di-tert-butyl-4-[1-oxido-4-(biphenyl-4-yl)-5,5-dimethyl-1H-imidazole-2(5H)-ylidene]cyclohex-2,5-dienone, its magnetic susceptibility, EPR spectra of the obtained hybrid radicals in solution, and cyclic voltammetry characteristics of 4H-imidazoles were studied.