Structure-property investigations of conjugated thiophenes fused onto a dehydro[14]annulene scaffold

A series of 12 thieno-fused macrocycles based on the dehydro14]annulene framework have been prepared. Studies have focused on the optical and electronic properties of the dehydrobenzothieno14]annulenes (DBTAs) and dehydrothieno14]annulenes (DTAs) utilizing NMR spectroscopy, UV-vis spectrophotometry, electrochemistry, and DFT computations. X-ray crystal structures were also obtained for two of the macrocycles. The structure-property relationships were found to vary significantly based on the relative orientation of the thiophenes. The stability, properties, and reactivity of these macrocycles were found to be more typical of dehydroannulenes rather than oligothiophenes.