Novel organic high-spin ions; The generation of the ground-state high-spin from the first prototypical intramolecular spin-frustrated system by thermal electron attachment

The first prototypical example of intramolecular (through-bond) spin frustrated systems, 4,4′,4″-tris (diphenylmethylene)amine, N(p-DPM)3 (S=l) and its mono anion, N(p-DPM)3−, was studied by ESR spectroscopy, emphasizing that the ground-state high-spin (S=3/2) for N(p-DPM)3, was generated in an organic glass, and that quantum nature of electron spin alignment in the spin-frustrated systems shows up. The experimentally determined fine-structure parameters of N(p-DPM)3− were to be ¦D¦=0.123cm−1 and ¦E¦=0.005cmN(p-DPM)3−, indicating that an excess electron occupies the in-plane nonbonding MO predominantly localized at the divalent carbon site and the molecular structure of N(p-DPM)3N(p-DPM)3− is non-C3 symmetric. The underlying mechanism controlling the spin alignment of the charged high-spin frustrated system is expounded by a VB description in terms of an MO calculation.