Structural isomers of di-p-benzidithiaoctaphyrins.

ABSTRACT

The cis and trans structural isomers of di-p-benzidithiaoctaphyrins were synthesized by adopting two different synthetic routes using readily available precursors under acid-catalyzed conditions, and the isomers were separated using basic alumina column chromatography. 1D and 2D NMR spectroscopy were used to deduce the molecular structures of the macrocycles, which also helps to differentiate the cis isomer from the trans isomer. DFT studies revealed that both the cis and trans isomers adopt figure of eight conformations but exhibit clear differences in their structural features, and the trans isomer is more distorted than the cis isomer. Experimental and theoretical studies revealed that both the cis and trans isomers are nonaromatic stable macrocycles and show subtle differences in their structure, spectral and redox properties. The cis and trans isomers of di-p-benzidithiaoctaphyrin exhibit nonaromatic absorption features in the visible-NIR region, and electrochemical studies revealed their electron-rich nature. TD-DFT studies are in agreement with the experimental observations.