Characterization and magnetic properties of a "super stable" radical 1,3-diphenyl-7-trifluoromethyl-1,4-dihydro-1,2,4-benzotriazin-4-yl.

Content Provider	Semantic Scholar
Author	Constantinides, Christos P. Koutentis, Panayiotis A. Krassos, Harry Rawson, Jeremy M. Tasiopoulos, Anastasios J.
Copyright Year	2011
Abstract	1,3-Diphenyl-7-trifluoromethyl-1,4-dihydro-1,2,4-benzotriazin-4-yl (4), prepared in high yield via the catalytic oxidation of the corresponding amidrazone 5 by using Pd/C (1.6 mol %) and 1,8-diazabicyclo[5.4.0]undec-7-ene (0.1 equiv) in air, is stable in dichloromethane solutions in the presence of MnO(2) and KMnO(4). Furthermore, radical 4 is thermally stable well past its melting point (160-161 °C) with a decomposition onset temperature of 288 °C. X-ray studies show that radical 4 packs in equidistant slipped π-stacks along the a axis. Cyclic voltammetry shows two fully reversible waves, corresponding to the -1/0, 0/+1 processes. EPR studies indicate that the spin density is mainly delocalized on the triazinyl fragment of the heterocycle. Magnetic susceptibility measurements in the 5-300 K region showed that the radical obeys Curie-Weiss behavior down to 10 K (C = 0.376 emu·K·mol(-1) and θ = +1.41 K) consistent with weak ferromagnetic interactions between S = 1/2 radicals. Subsequent fitting of the magnetic data to a 1D ferromagnetic chain model provided an excellent fit (g = 2.00, J/k = +1.49 K) down to 10 K but failed to reproduce the subsequent decrease in χT at lower temperatures, which has been ascribed to the onset of weaker antiferromagnetic interactions between ferromagnetic chains.
File Format	PDF HTM / HTML
DOI	10.1021/jo200210s
Alternate Webpage(s)	http://www2.ucy.ac.cy/~tasiopo/64.pdf
PubMed reference number	21384906
Alternate Webpage(s)	https://doi.org/10.1021/jo200210s
Journal	Medline
Volume Number	76
Issue Number	8
Journal	The Journal of organic chemistry
Language	English
Access Restriction	Open
Content Type	Text
Resource Type	Article