Corannulene is a multifaceted polyaromatic compound. It has many interesting properties; for example, it has a bowl‐shaped molecular structure that, in addition, undergoes a dynamic inversion process. It has attracted much attention within the last decades. This is not only due to its structural properties but also its electronic properties and its various potential applications to materials chemistry. Here, synthetic approaches towards corannulene derivatives with electron‐withdrawing substituents are summarized. This includes both selective and unselective methods. Further, the electrochemical properties, that is, the reduction potentials, are analyzed and compared. As a main conclusion, one can state that the electron affinity depends roughly linearly on the number of substituents. Finally, the structural behavior of the substituted buckybowls in the solid state is highlighted. This also allows a general statement about the influence of the electronic and steric nature of substituents on the molecular structures and the solid‐state packing of the corannulene derivatives.

Trifluoromethylthio-substituted corannulene can be easily synthesized in good yield by the reaction of iodocorannulene with CuSCF . Oxidation with meta-chloroperbenzoic acid (mCPBA) yields the corresponding sulfonyl compound which exhibits the largest anodic shift of the redox potential caused by a single substituent. Similarly, four SCF , SC F and SeC F substituents are introduced in the 1,2,5,6-positions of corannulene starting with 1,2,5,6-tetraiodo- or 1,2,5,6-tetrabromocorannulene, respectively. The reactions are performed in polar aprotic solvents and are believed to follow S Ar-type substitution mechanisms. Crystal and molecular structures of selected compounds were elucidated by X-ray crystallography. Trifluoromethanesulfonyl corannulene and the fourfold-substituted trifluoromethylthioether exhibit a perfect columnar stacking of the bowls. The substituted corannulenes were investigated electrochemically by cyclic voltammetry giving raise to large anodic shifts owing to substitution with electron-withdrawing groups.

Herein we report the synthesis of tetracyanocorannulene by a simple and clean reaction that in principle can be performed on a multigram scale. The tetranitrile can be transformed into corannulene‐fused imides with fluorinated substituents. The cyano compound as well as the imides were investigated structurally by X‐ray diffraction and electrochemically by cyclic voltammetry. Tetracyanocorannulene as well as the derived bis[(pentafluorophenyl)imide] proved to be corannulene compounds with a large electron affinity.

Herein, we report the preparation of silver(I) pentafluorooxosulfate from commercially available AgF and OSF 4 . The compound is surprisingly stable in a MeCN solution. Apart from that, AgOSF 5 has been stabilised by the addition of 2,2'-bipyridine ligands. Starting from solutions of the unstabilised silver(I) salt, OSF 5 complexes with Ni II , Cu I , and Cu II -centres have been obtained. In addition, AgOSF 5 has proven to be generally capable of mediating the transfer of OSF 5 groups to aryne moieties, thus furnishing a new and safe method for the preparation of OSF 5 -substituted arenes. X-ray crystal structure analysis of selected transition-metal OSF 5 compounds have revealed distorted octahedral [OSF 5 ] À anions which are extensively stabilised by hydrogen bonding.Scheme 1. Preparation of silver(I) pentafluorooxosulfate 3.

Herein we report general methods allowing the synthesis of various perfluoroalkylated corannulenes with a specific substitution pattern. Variable temperature NMR spectroscopic investigations revealed dynamic behavior which was analyzed by line shape analysis. The activation parameters of these dynamic processes were determined. For a tetrasubstituted compound it was possible to observe through space scalar coupling. The packing motifs were elucidated by X-ray crystallography, showing that the substitution pattern as well as the size of substituents strongly influence intermolecular π-stacking. The reduction potentials of the perfluoroalkylated compounds were determined by cyclic voltammetry.