Steering Scholl Oxidative Heterocoupling by Tuning Topology and Electronics for Building Thiananographenes and Their Functional N−/C−Congeners

While intramolecular Scholl oxidative coupling between two arenes is common, successful C−C heterocoupling between thiophene and arene is scarce. The latter is due to the notorious reactivity of thiophene towards polymerization under oxidative conditions. This report systematically demonstrates how topological variation of electronics and reactivity in thiophene substrates can lead to efficient oxidative heterocoupling. Bis(biaryl)thiophenes having reactive α- and β-positions open are the choice of substrates. The cyclizing arene partners are so electronically tuned for thiophene's reactivity (at α- and β-) as to establish C−C bond oxidatively generating symmetrical as well as unsymmetrical diphenanthrothiophenes which are basic thiananographenes. Depending on the cyclizing-couple's electronics, either arene- or thiophene-centered oxidation initiates C−C heterocoupling. The potential utility of these simple thiananographenes is further unfurled by converting them to functional N−/C-graphene segments that are aza-corannulene precursor and tetrabenzospirobifluorene. Their bright emission and extended electrochemical stability are remarkable that may be potentially important and applicable.