Akamptisomerism Beyond Porphyrins: Bond Angle Reflection and Stereochemical Divergences in Corrole- and Porphyrin-Anchored B-O-B Bridges.

ABSTRACT: Main-group coordination-driven porphyrins (MGCPs) are an emerging class of complexes featuring central main-group elements. Bis-boron(III) B₂OF₂-porphyrinoids, including porphyrins and corroles, exhibit a rich coordination chemistry with a (F)B-O-B(F) bridge bound to the N₄ core. Porphyrins adopt a transoid bridge, while corroles favor a cisoid arrangement. These systems enable investigation of akamptisomerism ─ an underexplored conformational isomerism driven by restricted bond angle reflection (BAR) at the oxygen bridge. Density functional theory was used to investigate cisoid/transoid preference, the BAR mechanism, and stabilization of the cisoid isomer via noncovalent interactions. Geometric and natural bond orbital an

SUBMITTER: de Andrade KN 

PROVIDER: S-EPMC12801324 | biostudies-literature | 2026 Jan

REPOSITORIES: biostudies-literature