Sequential Synthesis and Secondary Structure Analysis of Two Classes of Perylene Bisimide Oligomers.

An iterative step-by-step synthetic approach is employed to form perylene bisimide (PBI) oligomers of defined sizes by connecting the PBI units through their imide positions via a benzyl linker. The versatility of this approach was showcased by its successful implementation on two different PBI building blocks to achieve two separate series of oligomers (up to the pentamer) with modulated conformations: one with an open random coil oligomer and one with an H-type foldamer architecture.

Enantioselective Recognition of Helicenes by a Tailored Chiral Benzo[ghi]perylene Trisimide π-Scaffold.

Enantioselective molecular recognition of chiral molecules that lack specific interaction sites for hydrogen bonding or Lewis acid-base interactions remains challenging. Here we introduce the concept of tailored chiral π-surfaces toward the maximization of shape complementarity. As we demonstrate for helicenes it is indeed possible by pure van-der-Waals interactions (π-π interactions and CH-π interactions) to accomplish enantioselective binding. This is shown for a novel benzo[ghi]perylene trisimide (BPTI) receptor whose π-scaffold is contorted into a chiral plane by functionalization with 1,1'-bi-2-naphthol (BINOL). Complexation experiments of enantiopure (P)-BPTI with (P)- and (M)-[6]helicene afforded binding constants of 10 700 M-1 and 550 M-1 , respectively, thereby demonstrating the pronounced enantiodifferentiation by the homochiral π-scaffold of the BPTI host. The enantioselective recognition is even observable by the naked eye due to a specific exciplex-type emission originating from the interacting homochiral π-scaffolds of electron-rich [6]helicene and electron-poor BPTI.