Реферат: A series of 3-trifluoromethyl-substituted Blatter radicals was synthesized and fully characterized. 1-(4-Iodophenyl)-3-(trifluoromethyl)-1,4-dihydrobenzo[e][1,2,4]triazine-4-yl was obtained in good yield by the oxidation of the corresponding amidrazones using MnO2 in THF in the presence of Et3N. The resulting iodo derivative was subjected to a cross-coupling reaction with trimethylsilylacetylene in the presence of a catalytic amount of [Pd(PPh3)2Cl2] and CuI, affording the 3-(trifluoromethyl)-1-(4-((trimethylsilyl)ethynyl)phenyl) derivative in 80% yield. Next, the trimethylsilyl protecting group was removed under mild conditions in methanol using K2CO3 as a base, yielding 3-(trifluoromethyl)-1-(4-(ethynyl)phenyl)-1,4-dihydrobenzo[e][1,2,4]triazine-4-yl in an 85% yield. Cross-coupling of the Blatter iodo derivative with this acetylene compound yielded a conjugated diradical. Moreover, a rigid Blatter diradical with a longer conjugated linker was prepared by cross-coupling the acetylene derivative with 1,4-diiodobenzene under similar conditions. Cyclic voltammetry revealed that both radicals and diradicals undergo reversible electrochemical oxidation and reduction, corresponding to the redox processes −1/0 and 0/+1. The molecular and crystal structures of the iodine and acetylene derivatives were determined using single-crystal X-ray diffraction (XRD). XRD analysis and DFT calculation showed that the iodine derivatives form dimers in the solid state, for which the structure and exchange interaction parameters exhibit significant temperature-dependent changes in the range of 100–296 K. In contrast, the acetylene derivative forms shifted π-stacks. Magnetic susceptibility measurements in the range 2–300 K demonstrated that strong antiferromagnetic interactions dominate in both crystals. Fitting the χT vs T dependence for compound 5 yielded the following best-fit parameters: g = 2.09 ± 0.01, J/kB = −234 ± 2 K. For compound 3 (alpha-modification), low- and high-temperature parameters were estimated: JLT/kB = −267 ± 17 K and JHT/kB = −105 ± 2 K, respectively. In conclusion, a general analysis of the magnetism of substituted 1-phenyl-3-trifluoromethyl Blatter radicals is presented.

Библиографическая ссылка: Stepanov A.V. , Zlokazov M.V. , Gadimov N.V. , Shashkov A.V. , Sosunov E.A. , Syroeshkin M.A. , Romanenko G.V. , Bogomyakov A.S. , Gorbunov D.E. , Gritsan N.P. , Tretyakov E.V.
Synthesis, Structure, and Magneto-Structural Correlations in 1-Phenyl-3-trifluoromethyl-Substituted Blatter Radicals
Crystal Growth and Design. 2026. V.26. N14. P.5657-5670. DOI: 10.1021/acs.cgd.6c00615 WOS OpenAlex

Даты:

Поступила в редакцию:	2 мая 2026 г.
Принята к публикации:	16 июн. 2026 г.
Опубликована online:	23 июн. 2026 г.
Опубликована в печати:	15 июл. 2026 г.

Идентификаторы БД:

≡ Web of science:	WOS:001800608600001
≡ OpenAlex:	W7165631218

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