Structural, Magnetic, and Computational Correlations of Some Imidazolo-Fused 1,2,4-Benzotriazinyl Radicals

摘要

1,3,7,8-Tetraphenyl-4,8-dihydro-1H-imidazolo[4,5g]-[1,2,4]benzotriazin-4-yl (5), 8-(4-bromophenyl)-1,3,7-triphen-yl-4,8-dihydro-1 H-imidazolo[4,5g][1,2,4]benzotriazin-4-yl (6), and 8-(4-methoxyphenyl)-1,3,7-triphenyl-4,8-dihydro-1 Himidazolo[4,5g][1,2,4]benzotriazin-4-yl (7) were characterized by using X-ray diffraction crystallography, varia ble-temperature magnetic susceptibility studies, and DFT calculations. Radicals 5-7 pack in 1 D π stacks made of radical pairs with alternate short and long interplanar distances. The magnetic susceptibility (X vs. T) of radicals 5 and 6 exhibit broad maxima at (50±2) and (50 ±4) K, respectively, and are interpreted in terms of an alternating antiferro magnetic Heisen-berg linear chain model with average exchange-interaction values of J=-31.3 and -35.4cm~(-1) (g_(solid) = 2.0030 and 2.0028) and an alternation parameter a = 0.15 and 0.38 for 5 and 6, respectively. However, radical 7 forms 1 D columns of radical pairs with alternating distances; one of the interplanar distances is significantly longer than the other, which decreases the magnetic dimensionality and leads to discrete dimers with a ferromagnetic exchange interaction between the radicals (2J = 23.6 cm~(-1), 2zJ'= -2.8 cm~(-1), g_(solid) =2.0028). Magnetic exchange-coupling interactions in 1,2,4-benzotria-zinyl radicals are sensitive to the degree of slippage and inter-radica I separation, and such subtle changes in structure alter the fine balance between ferro- and antiferro magnetic interactions.