The reaction of 5,10,15-trimesitylcorrole (H3 cor) with tungsten hexachloride and tungsten hexacarbonyl resulted in the unexpected formation of the 3,17-dichloro-5,10,15-trimesitylcorrole radical (H2 cor*) as an air-stable product. X-ray crystallography proved the planarization of the corrole radical structure, which was rationalized by the reduced steric hindrance of two versus three hydrogen atoms inside the N4 cavity. Although the aromaticity was lost, no specific changes in C-C or C-N bond distances could be observed. The regioselectivity of the two-fold chlorination is the result of the nucleophilic attack of chloride ions to an oxidized corrole macrocycle, and is supported by DFT results. The corrole radical acts as a dianionic ligand and allows the insertion of the divalent zinc(II) cation, which usually does not form neutral corrole complexes.

Nickel, palladium, and copper complexes of the tripyrrolic ligand hexaethyltripyrrindione (H 3 Et 6 tpd, 1) have been prepared and characterized by UV/Vis and EPR spectroscopy, as well as by single-crystal X-ray structure determination. In all cases the metal ion is coordinated in a distorted square-planar geometry carrying a water ligand at the fourth coordination site. The Et 6 tpd ligand acts as a radical dianion in all cases. In solution, monomeric species are present in which the open-

The reaction of 5,10,15-trimesitylcorrole (H 3 cor) with tungsten hexachloride and tungsten hexacarbonyl resulted in the unexpected formation of the 3,17-dichloro-5,10,15trimesitylcorrole radical (H 2 cor*) as an air-stable product. Xray crystallography proved the planarization of the corrole radical structure,whichwas rationalized by the reduced steric hindrance of two versus three hydrogen atoms inside the N 4 cavity.A lthough the aromaticity was lost, no specific changes in C À Co rC À Nb ond distances could be observed. The regioselectivity of the two-fold chlorination is the result of the nucleophilic attacko fc hloride ions to an oxidized corrole macrocycle,a nd is supported by DFT results.T he corrole radical acts as adianionic ligand and allows the insertion of the divalent zinc(II) cation, which usually does not form neutral corrole complexes.

Nickel(II) complexes of ring-contracted 9-methylisocorroles were prepared by templated macrocyclisation and act as the first porphyrinoid catalysts for C–C cross-coupling.

BODIPY DYEmers with dithioaryl bridges have been prepared by nucleophilic substitution reactions of α‐brominated BODIPYs. The optical properties of these compounds can be predicted by the Kashas exciton coupling model up to a critical interchromophore distance. The first macrocyclic derivative with stacked subchromophores has been obtained and proves the suitability of the Kasha model for predicting H‐type behavior from the molecular structures of this type of DYEmer.