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Tuning the Electron Affinity and Stacking Properties of Corannulene by Introduction of Fluorinated Thioethers
Author(s) -
Haupt Axel,
Lentz Dieter
Publication year - 2018
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201801311
Subject(s) - corannulene , chemistry , stacking , substituent , yield (engineering) , cyclic voltammetry , crystallography , redox , medicinal chemistry , electrochemistry , molecule , organic chemistry , electrode , materials science , metallurgy
Trifluoromethylthio‐substituted corannulene can be easily synthesized in good yield by the reaction of iodocorannulene with CuSCF 3 . Oxidation with meta ‐chloroperbenzoic acid ( m CPBA) yields the corresponding sulfonyl compound which exhibits the largest anodic shift of the redox potential caused by a single substituent. Similarly, four SCF 3 , SC 6 F 5 and SeC 6 F 5 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 N 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.