Electron-Accepting Dithiarubicene (Emeraldicene) and Derivatives Prepared by Unprecedented Nucleophilic Hydrogen Substitution by Alkyllithium Reagents

• Published in: Chemistry : a European journal Vol. 17; no. 9; pp. 2642 - 2646
• Main Authors: Mohebbi, Ali Reza, Wudl, Fred
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 25.02.2011; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Subjects: Alkylation; Chemistry; Chemistry, Multidisciplinary; Crystallization; Derivatives; Electronics; emeraldicene; Heck reaction; Hydrides; nucleophilic aromatic alkylation; organic acceptor; Physical Sciences; polycyclic heteroaromatic hydrocarbon; Science & Technology; Solvents; Stacks; Switching; polycyclic heteroaromatic hydrocarbon; ACENES; POLYCYCLIC AROMATIC-HYDROCARBONS; ALKYLATION; Heck reaction; emeraldicene; nucleophilic aromatic alkylation; FRAGMENTS; CYCLIZATIONS; ORGANIC ELECTRONICS; ARYL HALIDES; organic acceptor; RUBICENES
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201002608

By understanding the role of DMF as a hydride source via a Pd‐catalyzed reaction and switching to CH3CN solvent, an efficient route for the synthesis of emeraldicene and some new substituted derivatives is reported with potential application in organic electronics. Additionally, the nucleophilic alkylation of emeraldicene 4 a with alkyllithium reagents provides monosubstituted compounds 7 a and 7 b, the latter crystallizing in columnar stacks, with π–π overlap between adjacent molecules in the stack. Great potential: New derivatives of dithiarubicene (emeraldicene), which are of potential use as organic acceptors, are reported (see figure, R = ‐H, ‐dodecyl, ‐ethylhexyl). Additionally, nucleophilic aromatic hydrogen displacement alkylation of emeraldicene by alkyllithium reagents produced highly soluble mono‐substituted emeraldicene, which crystallized in columnar stacks, with excellent overlap between adjacent molecules in the stack.