Norroles are isomers of corroles containing a direct pyrrole N–pyrrole C link instead of a pyrrole C–pyrrole C link of corroles. 22-Oxanorroles are core-modified norroles in which one of the pyrroles is replaced with a furan ring. A straightforward route is adopted to synthesize the first examples of aromatic meso-triaryl-22-oxanorroles containing a pyrrole N–pyrrole α-C direct bond in 4–7% yields by condensing 16-oxatripyrrane and (1H-pyrrol-3-yl)­(p-tolyl)­methanol in CH2Cl2 under mild acid-catalyzed conditions followed by oxidation with DDQ.

The first examples of meso-triaryl 22-oxabenzonorroles were synthesized in 18-21% yields by oxidation of appropriate meso-triaryl oxabenzobilane. The key precursors, the meso-triaryl oxabenzobilanes were synthesized readily by treating 16-oxatripyrrane with (1H-indol-3-yl)(ptolyl)methanol under acid catalyzed conditions. The mesotriaryl 22-oxabenzonorroles were obtained in free base form by following our simple straight-forward synthetic strategy. The X-ray structure obtained for meso-tritolyl 22-oxabenzonorroles revealed that the indole ring was deviated by an angle of 41.27°from the mean plane. The NMR studies supported the presence of diatropic ring current effect as inner NH and CH protons were observed in the upfield region. The absorption spectra of 22-oxabenzonorroles exhibited one strong Soret band and four weak Q-bands. The electrochemical studies revealed that the macrocycles are electron rich and undergo easier oxidations. The DFT and TD-DFT studies were in agreement with the experimental observations and NICS and HOMA values supports the aromatic nature of meso-triaryl oxabenzonorroles.

Oxidative cyclization of open chain thiabilanes yielded the first examples of unique piperazine bridged thianorrole dimers instead of the expected thianorrole monomer. In the thianorrole dimer, the two thianorrole monomeric units are linked via two direct pyrrole C–C bonds by involving the inverted pyrrole and adjacent pyrrole rings of each thianorrole macrocycle and generate a six-membered piperazine ring that bridges the two thianorrole macrocycles. The spectral studies indicated that the thianorrole dimers are nonaromatic in nature.

Three examples of moderately aromatic p-benzi dithiasapphyrin and p-benzi tellurathiasapphyrins have been synthesized by condensing p-benzithiophene diol with 16-thia/ telluratripyrrane under acid-catalyzed reaction conditions. The Xray structural analysis showed that the thiophene ring in p-benzi dithiasapphyrin was inverted, whereas the tellurophene ring in pbenzi tellurathiasapphyrins was normal conformation with respect to the macrocyclic core. However, NMR studies revealed that the thiophene ring in protonated p-benzi dithiasapphyrin flips to normal, whereas the tellurophene ring in p-benzi tellurathiasapphyrins flips to inverted orientation.