A porphyrinogen macrocycle incorporating two azulenes, phenylene and thiophene into the framework, joined by four C(sp ) atoms has been obtained as a mixture of six isomers. They were successfully separated and characterized spectroscopically. The identity of two of them was confirmed by X-ray crystallography. One isomer was tested in reaction with [Ru (CO) ] yielding exclusively π-complex with two clusters attached to azulenes. The partial oxidation of porphyrinogens yielded dication with two unmodified meso bridges. The stepwise oxidation followed by reaction with water as nucleophile afforded the dicationic species with two hydroxyl groups and a trication with one OH group. The hydroxy-dication can be reversibly transformed into hydroxy-trication by addition of HBF etherate.
Diazuli‐p‐benzithiaporphyrinogens and their oxidized polycarbocationic forms provide intriguing examples of azuliporphyrinoids that incorporate the p‐phenylene unit into the macrocyclic framework of expanded porphyrinoid. In their manuscript, L. Latos‐Grażyński and co‐workers also demonstrated that these hybrid macrocycles can acquire a role of a conformationally flexible carbon platforms, that possess well established π‐coordination properties toward tetrahedral Ru4(CO)9 clusters, confined in the original macrocyclic architecture. More information can be found in the Full Paper by N. Sprutta, L. Latos‐Grażyński et al. on page 14686.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.