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 (Cp2Cr+)(H+)(H2TPCor˙2-)·C6H4Cl2

• Published in: Dalton transactions : an international journal of inorganic chemistry 2017, Vol.46 (40), p.13994-14001
• Main Authors: Konarev, Dmitri V, Karimov, Dmitri R, Khasanov, Salavat S, Shestakov, Alexander F, Otsuka, Akihiro, Yamochi, Hideki, Kitagawa, Hiroshi, Lyubovskaya, Rimma N
• Format: Article
• Language: English
• ISSN: 1477-9234
• DOI: 10.1039/c7dt02901b

The reduction of 5,10,15-triphenylcorrole (H3TPCor) with decamethylchromocene yields (Cp*2Cr+)(H+)(H2TPCor˙2-)·C6H4Cl2 (1). It is accompanied by the deprotonation of H3TPCor and the formation of planar H2TPCor˙2- radical dianions. Complex 1 manifests a band at about 750 nm observed in the solution spectra of H2TArylCor˙2- and demonstrates an EPR signal attributed to the reduced corrole macrocycle. The magnetic moment of 1 of 4.10μB at 300 K indicates the contribution of Cp*2Cr+ (S = 3/2) and H2TPCor˙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 H2TPC˙2- dianions from the deprotonated H2TPCor- anions, we also studied the {cryptand[2,2,2](Na+)}(H2TPCor-)·0.5C6H4Cl2 (2) salt with deprotonated corrole anions. In this case, a planar macrocycle was formed as well. However, the properties of H2TPCor- in 2 differ from those of H2TPCor˙2- in 1.