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 (Cp*Cr)(H)(HTPCor˙)·CHCl.

The reduction of 5,10,15-triphenylcorrole (HTPCor) with decamethylchromocene yields (CpCr)(H)(HTPCor˙)·CHCl (1). It is accompanied by the deprotonation of HTPCor and the formation of planar HTPCor˙ radical dianions. Complex 1 manifests a band at about 750 nm observed in the solution spectra of HTArylCor˙ and demonstrates an EPR signal attributed to the reduced corrole macrocycle. The magnetic moment of 1 of 4.10μ at 300 K indicates the contribution of CpCr (S = 3/2) and HTPCor˙ (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 HTPC˙ dianions from the deprotonated HTPCor anions, we also studied the {cryptand2,2,2}(HTPCor)·0.5CHCl (2) salt with deprotonated corrole anions. In this case, a planar macrocycle was formed as well. However, the properties of HTPCor in 2 differ from those of HTPCor˙ in 1.