Solid state structures and properties of free-base 5,10,15-triphenylcorrole (TPCor) anions obtained by deprotonation and reduction. Effective magnetic coupling of spins in (CpCr)(H)(HTPCor&z.rad;)·CHCl

The reduction of 5,10,15-triphenylcorrole (H 3 TPCor) with decamethylchromocene yields (Cp* 2 Cr + )(H + )(H 2 TPCor&z.rad; 2− )·C 6 H 4 Cl 2 ( 1 ). It is accompanied by the deprotonation of H 3 TPCor and the formation of planar H 2 TPCor&z.rad; 2− radical dianions. Complex 1 manifests a band at about 750 nm observed in the solution spectra of H 2 TArylCor&z.rad; 2− and demonstrates an EPR signal attributed to the reduced corrole macrocycle. The magnetic moment of 1 of 4.10 μ B at 300 K indicates the contribution of Cp* 2 Cr + ( S = 3/2) and H 2 TPCor&z.rad; 2− ( S = 1/2). These paramagnetic species alternate in the π-stacks providing rather effective antiferromagnetic coupling of spins at the Weiss temperature of −31 K. To distinguish the H 2 TPC&z.rad; 2− dianions from the deprotonated H 2 TPCor − anions, we also studied the {cryptand[2,2,2](Na + )}(H 2 TPCor − )·0.5C 6 H 4 Cl 2 ( 2 ) salt with deprotonated corrole anions. In this case, a planar macrocycle was formed as well. However, the properties of H 2 TPCor − in 2 differ from those of H 2 TPCor&z.rad; 2− in 1 . The structures and properties of free-base triphenylcorrole radical H2TPCor&z.rad; 2− dianions and diamagnetic deprotonated H2TPCor − anions have been studied. In both cases, deprotonation provides a planar shape of the corrole macrocycle. High-spin Cp* 2 Cr + ( S = 3/2) and H2TPCor&z.rad; 2− with the S = 1/2 spin state alternate in the π-stacks providing effective antiferromagnetic coupling of spins.