Towards the Highly Efficient Synthesis and Selective Methylation of C(sp3)-Bridged [6]Cycloparaphenylenes from Fluoren[3]arenes

An approach to the highly efficient synthesis of C(sp3)-bridged [6]cycloparaphenylenes (C[6]CPPs) from fluoren[3]arenes (F[3]As) was developed. Consequently, F[3]As as a new kind of macrocyclic arenes were synthesized. Followed by the demethylation, triflation and intramolecular aryl-aryl coupling reactions, C[6]CPPs were then conveniently obtained. Interestingly, C[6]CPPs could be selectively methylated to produce their fully outer-methyl-substituted derivatives. The crystal structures showed the hydroxyl-substituted F[3]As had bowl-shaped conformations, and the C[6]CPPs exhibited rigid belt-shaped structures with deep cavities. Moreover, C[6]CPPs exhibited high HOMO energies and narrow energy gaps. An unclosed belt was further obtained, and it not only showed a similar narrow energy gap to those of the aromatic belts, but also displayed strong fluorescence property, which can play a vital role in the design and synthesis of new aromatic belts.

Automated summary

An efficient method for the synthesis of C(sp3)-bridged [6]cycloparaphenylenes (C[6]CPPs) from fluoren[3]arenes (F[3]As) has been developed, resulting in the synthesis of a new type of macrocyclic arenes. C[6]CPPs exhibit rigid belt-shaped structures and can be selectively methylated to produce fully outer-methyl-substituted derivatives. This research also obtained an unclosed belt with narrow energy gaps and strong fluorescence property, offering potential for the design and synthesis of new aromatic belts.