Abstract: | New triphenylamine derivatives 1, 2, 3, and 4 were synthesized and characterized by IR, FAB‐MS, EPR and EA. All of them displayed similar absorption and fluorescence spectra except compound 1, for which a possible explanation was proposed. Quasi‐reversible oxidation waves at about 0.76 V (vs. SCE) and 1.1 V for nitronyl nitroxide and iminyl nitroxide respectively as well as irreversible one at about 1.5 V for triphenylamine group were detected with cyclic voltammetry for compounds 1, 2, 3 and 4. Crystal structures of 2 and 4 were determined by X‐ray diffraction analysis. Their crystal data are as follows: for 2: monoclinic, C2/c, a = 1.69914 (4), b = 1.37435(5), c = 1.24621(5) ran, β= 106.553(2)°, V = 2.7896(2) nm3 Z = 4; for 4: orthorhombic, Pbca, a = 1.95970(6), b = 1.33096(4), c = 4.84691(14) nm, V = 12.6421(7) nm3, Z = 8. Magnetic studies indicated that all of them showed antiferromagnetic properties in solid state, but with strong intermolecular spin‐spin coupling as indicated by the relatively large values of 6, in particular for 4 (θ = ?12 K). Possible spin‐spin interaction mechanism was suggested based on the crystal structures of 2 and 4. |