Discovery of an all-donor aromatic [2]catenane

Abstract

We report herein the first all-donor aromatic [2]catenane formed through dynamic combinatorial chemistry, using single component libraries. The building block is a benzo[1,2-b:4,5-b’]dithiophene derivative, a p-donor molecule, with cysteine appendages that...

Dynamic Covalent Chemistry for Synthesis and Co‐conformational Control of Mechanically Interlocked Molecules

“…[68] The Pantoş group recently reported the expansion of these systems with cysteine-linked benzodithiophene derivatives. [69] When exposing such electron-rich aromatic systems to disulfide forming oxidative conditions, only dimeric macrocycles were initially observed. However, by increasing ionic strength of the aqueous solution and thus strengthening the hydrophobic effect, an all-donor [2]catenane, composed of four stacked Hopf link (left), a Solomon link (middle) and a trefoil 3 1 knot (right) as a result of the hydrophobic effect.…”

“…The Pantoş group recently reported the expansion of these systems with cysteine‐linked benzodithiophene derivatives [69] . When exposing such electron‐rich aromatic systems to disulfide forming oxidative conditions, only dimeric macrocycles were initially observed.…”

Dyn[n]arenes: Versatile Platforms To Study the Interplay between Covalent and Noncovalent Bonds

“…This thermodynamic lability was exploited by Sanders et al [30–32] . and others [21,33–35] to obtain topologically complex architectures and receptors in aqueous media. During self‐assembling in aqueous solutions, the slow oxidation of the thiols competes with the disulfide exchange (Figure 2i).…”

“…Disulfide bond formation and exchange occur spontaneously in aqueous solution at pH between 7 and 9, and may be quenched by lowering the pH below the pK a of the thiols involved. This thermodynamic lability was exploited by Sanders et al [30][31][32] and others [21,[33][34][35] to obtain topologically complex architectures and receptors in aqueous media. During selfassembling in aqueous solutions, the slow oxidation of the thiols competes with the disulfide exchange (Figure 2i).…”

Template-Free Synthesis of an Interlocked Covalent Organic Molecular Cage

“…Mechanically interlocked molecules (MIMs) have attracted significant interest not only due to their aesthetically beautiful structures but also the unique properties originating from their interlaced nature. − It has been proven that MIMs like structures have inextricably woven into the life processes. − To obtain more insight into natural processes, artificial analogues are often created to help in better understanding the role of such topologies. Although remarkable progress has been achieved in recent years, the synthesis of MIMs such as catenanes, rotaxanes, Borromean rings, knots, and interlocked cages remains a synthetic challenge. − The rise of template synthesis , and reversible metal coordination bonds − have to a large extent overcome this limitation. Several successful examples for the preparation of such topologies through coordination have been reported. , Therein template synthesis requires multiple steps or late template removal.…”