Conformation-Dependent Response to Protonation of Diphenanthrioctaphyrin(1.1.1.0.1.1.1.0) - A Route to Pseudorotaxane-like Structures.

Conformation-Dependent Response to Protonation of Diphenanthrioctaphyrin(1.1.1.0.1.1.1.0) - A Route to Pseudorotaxane-like Structures.
Chemistry. 2020 Mar 23;:
Authors: Szyszko B, Przewoznik M, Bialek MJ, Bialonska A, Chmielewski P, Latos-Grazynski L
Abstract
Diphenanthrioctaphyrin(1.1.1.0.1.1.1.0), an expanded carbaporphyrinoid incorporating two phenanthrenylene moieties, exists as two separate, yet interconvertible, locked stereoisomers. These species demonstrate complex dynamic behavior upon protonation, consisting of multiple conformational rearrangements and anion-binding events. Formation of one of the final dicationic forms is accompanied by an inclusion of a complex anion(s) within the macrocyclic cavity yielding a pseudorotaxane-like host-guest complex. Protonation with trifluoroacetic or dichloroacetic acids followed by neutralization afforded the conformation-switching cycle which involves six structurally different species. Analogous acidification with chiral 10-camphorsulfonic acid and subsequent neutralization generated one of the free base stereoisomers with enantiomeric excess. Therefore, it was showed that a simple acid-base chemistry of diphenanthrioctaphyrin can be a stimuli inducing chirality into the system, allowing for manipulation of the stereochemical information imprinted into enantiomers of the macrocycle.
PMID: 32203626 [PubMed - as supplied by publisher]

Source: Chemistry - March 22, 2020 Category: Chemistry Authors: Szyszko B, Przewoznik M, Bialek MJ, Bialonska A, Chmielewski P, Latos-Grazynski L Tags: Chemistry Source Type: research