Diphenanthrioctaphyrin(1.1.1.0.1.1.1.0): Conformational Switching Controls the Stereochemical Dynamics of the Topologically Chiral System

Abstract

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.

Polycyclic Aromatic Hydrocarbon‐/Heterocycle‐Embedded Porphyrinoids

“…Latos-Grażyński and co-workers synthesized diphenanthrioctaphyrin(1.1.1.0.1.1.1.0) 78 a-b as shown in Scheme 20. [36] The 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 tripyrrane 44 was condensed with appropriate aldehydes under mild acid-catalyzed conditions to afford diphenanthrioctaphyrin 78 a-b in 6-13% yields. Interestingly authors have isolated two different structural conformers 78 a' and 78 a'' (Figure 7) by column chromatography and characterized by X-ray crystallography.…”

“…Latos‐Grażyński and co‐workers synthesized diphenanthrioctaphyrin(1.1.1.0.1.1.1.0) 78 a – b as shown in Scheme . The tripyrrane 44 was condensed with appropriate aldehydes under mild acid‐catalyzed conditions to afford diphenanthrioctaphyrin 78 a – b in 6–13% yields.…”

Conformation‐Dependent Response to the Protonation of Diphenanthrioctaphyrin(1.1.1.0.1.1.1.0): A Route to Pseudorotaxane‐Like Structures

“…[6][7][8][9] Even thought hey have been thoroughly studied for many decades, relatively little attention has been devoted to systems incorporating carbon atoms within the macrocyclic cavity,t hat is, expanded carbaporphyrinoids. [10,11] The growingi nterest that these macrocyclesh aves tarted to receive results from their intriguing electronic structures, [12][13][14] peculiar reactivity, [15] Mçbiusa romaticity, [16][17][18] stereochemical properties, [15,19] and, finally,t heir conformational flexibility. [20,21] Recently,a na lluring area of research has flourished employing expanded carbaporphyrinoids for the constructiono fs upramolecular systems.…”

Expandierte Carbaporphyrinoide

“…Die Kondensation des gleichen Phenanthritripyrran-Bausteins,d er fürd ie Synthese der Helicenophyrine verwendet wurde,m it Perfluorbenzaldehyd und p-Nitrobenzaldehyd und die anschließende DDQ-Oxidation lieferten das Diphenanthrioctaphyrin 191 (Schema 31). [153] Unerwarteterweise ergaben sich zwei separate Stereoisomere mit deutlich unterschiedlichen Eigenschaften, einschließlich unterschiedlicher elektronischer Absorptionsspektren. Cammidge und Mitarbeiter synthetisierten triphenylenhaltige Makrocyclen und untersuchten deren supramolekulare Eigenschaften, unter anderem Selbstorganisation und die Fähigkeit, flüssigkristalline Phasen zu bilden.…”

“…Ausgewählte expandierte Carbaporphyrinoide,z um Beispiel die Diphenanthrioctaphyrine 191-A und 191-B, weisen einzigartige konformative und stereodynamische Eigenschaften auf,a ufgrund derer sie als geeignete Plattform für die Speicherung und Manipulation von stereochemischen Informationen betrachtet werden sollten. [153] Schließlich scheint eine wichtige Richtung bei der Erforschung der expandierten Carbaporphyrinoide der Aufbau von supramolekularen Systemen zu sein. So wurde kürzlich ein innovatives Konzept fürk ovalente Käfige 197 vorgestellt, die unter Verwendung von expandierten Dibenzo[g,p]chrysencarbaporphyrinoiden aufgebaut wurden.…”