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Abstract

Introduction of tert-butyl groups into the phenazine frame-work was accomplished by treatment of 5-acetyl-5,10-dihydrophenazine (2a) with tert-butyl chloride in the presence of AlCl3. Starting from the 2,8- or 3,7-di-tert-butyl-substituted derivatives 2c and 2b, a series of phenazin-5(10H)-yl radicals (1c–i) was synthesized and characterized by ESR and EN-DOR spectroscopy. With the exception of 1c, all phenazin-5(10H)-yls were obtained in crystalline form, and for 1d–f the long-wavelength absorption band at λ ≈ 870 nm indicates intermolecular π-π interactions in the solid state. For 1d, 1e and 1h the crystal structure could be determined. The unit cell of 1d consists of eight phenazin-5(10H)-yls. Surprisingly, four of them are arranged in radical pairs, whereas the other four lie independently in the lattice. In agreement with this structure, the magnetic susceptibility results correspond to a content of 50% monoradical and an almost complete spinpairing in the radical pairs up to T = 220 K. In 1e, the four phenazin-5(10H)-yls in the unit cell are arranged in two independent radical pairs, A and B, which are characterized by close interplanar distances and short intermolecular contacts between atoms with significant spin populations. Accordingly, the susceptibility data indicate strong spin-pairing at low temperature. Due to extensive steric shielding of the phenazin-5(10H)-yl framework, the crystal structure of 1h gives no evidence of any π-π interactions between adjacent radicals. As expected, the magnetic susceptibility of 1h corresponds to that of an ordinary monoradical.