The analogue of octaphyrin(1.1.1.0.1.1.1.0) bearing two dimethoxyphenanthrene units was synthesized and characterized in solution and solid state. The macrocycle was demonstrated to exist as two locked conformers that can be easily separated and handled individually. The conversion of conformers was proven to be facilitated by the presence of hydrogen-bond acceptors, such as amines. The bis-boron(III) complex of diphenanthrioctaphyrin has been obtained, proving that the metalloid center acts as the topology selector stabilizing only one conformation of the macrocycle, irrespective of the stereoisomer used for the insertion. Both conformers of diphenanthrioctaphyrin, as well as the boron complex formed from them, have been separated into enantiomers using HPLC with a chiral stationary phase. All of these systems have shown strikingly different stereodynamic behavior.

Incorporation of phenanthrene into a hexaphyrin(1.1.1.1.1.0) frame resulted in intramolecular ring fusion, thus giving rise to chiral helicenophyrins. These molecules contain helicene and porphyrin features by incorporating either an aza[5]helicene or heptacyclic S-shaped aza[5]helicene.

, an expanded carbaporphyrinoid incorporating two phenanthrenylene moieties, exists as two separate, yet interconvertible, locked stereoisomers. These species demonstrate complex dynamic behavior upon protonation, consisting in multiple conformational rearrangementsa nd anion-binding events. The formation of one of the final dicationic formsi sa ccompanied by the inclusion of ac omplex anion(s) within the macrocyclic cavity yieldingapseudorotaxane-like host-guest complex. Protonation with trifluoroacetic or dichloroacetic acids followed by neutralization afforded ac onformation-switching cycle, which involves six structurally different species. Analogous acidification with chiral 10-camphorsulfonic acid and subsequentn eutralization generated one of the free base stereoisomers with enantiomeric excess. Therefore, it was shown that the simple acid-basec hemistry of diphenanthrioctaphyrin can act as stimulus,i nducing chirality into the system,a llowing for the manipulation of the stereochemical information imprinted into the enantiomerso ft he macrocycle.

Incorporation of phenanthrene into ah exaphyrin(1.1.1.1.1.0) frame resulted in intramolecular ring fusion, thus giving rise to chiral helicenophyrins.T hese molecules contain helicene and porphyrin features by incorporating either an aza[5]helicene or heptacyclic S-shaped aza[5]helicene.

The carbaporphyrinoid rollercoaster: Diphenanthrioctaphyrin(1.1.1.0.1.1.1.0) exists as two locked figure‐eight isomers that demonstrate multiple conformational rearrangements and anion‐binding events upon protonation. Formation of one of the final dications is accompanied by an inclusion of a complex anion within the cavity yielding a pseudorotaxane‐like complex. Multiple conformational transformations of the macrocycle remind the movement of a rollercoaster along a complex track constructed of loops and turns, providing the expanded carbaporphyrinoid amusement park. More information can be found in the Full Paper by B. Szyszko, L. Latos‐Grażyński, et al. on page 8555.