Tetracyclo(2,7-carbazole)s: Diatropicity and Paratropicity of Inner Regions of Nanohoops

Abstract

Three N-substituted tetracyclo­(2,7-carbazole)­s were synthesized to investigate the inner regions of nanohoops. One compound has a 5,5-dimethylnonane bridge between two neighboring <i>anti</i>-carbazoles, which can be used as covalently bonded “methane probes”. These probes near the ring center are strongly shielded by local ring currents and exhibit a singlet at δ = −2.70 ppm in ¹H NMR. To visualize local and macrocyclic ring currents separately, we drew nucleus-independent chemical shift contour maps of tetracyclo­(9-methyl-2,7-carbazole) and [<i>n</i>]­cycloparaphenylenes (CPPs). Local ring currents make the interior diatropic, and paratropic regions exist only outside the ring. Macrocyclic ring currents in [5]­CPP to [7]­CPP generate deshielding cones, which are typical of antiaromatic [4<i>n</i>]­annulenes