Self‐Sorting of Four Organic Molecules into a Heterowheel Polypseudorotaxane

Abstract

The social self-sorting supramolecular assembly is described by non-covalent interactions among four organic components. Toward this goal, a series of self-sorting systems have been investigated by mixing two or three different compounds; naphthyl-bridged bis(α-cyclodextrin), N,N'-dioctyl-4,4'-bipyridinium, 2,6-dihydroxynaphthalene, and cucurbit[8]uril. The influence of alkyl chains of viologen derivatives and the binding abilities of these systems have also been studied. Their integrative self-sorting led to the exclusive formation of the purple supramolecular heterowheel polypseudorotaxane. The heterowheel polypseudorotaxane is a thermodynamically stable self-sorted product, and consists of two different macrocycles with three sorts of different non-covalent interactions. Its structure was established by NMR spectroscopy and UV/Vis absorption spectroscopy, transmission electron microscopy (TEM), atomic force microscopy (AFM), dynamic light-scattering (DLS), diffusion-ordered spectroscopy (DOSY), and viscosity measurements.

Integrative Self‐Sorting in a Three Component System Leading to Formation of Long Fibrous Structures

“…During the last decade several reports dealing with self‐sorting processes in synthetic systems have appeared in the literature. In most of the artificial self‐sorting cases, formation of multiple assemblies in a mixture is the theme, but few cases where self‐sorting resulted in the formation of a single aggregate as in biological assemblies are also available . In this communication we report and analyze the self‐assembly and integrative self‐sorting processes observed in an aqueous solution containing a 2:1:1 mixture of native β‐cyclodextrin (β‐CD), a bis‐adamantane derivative AD‐AD and a bis‐pyromellitic diimide derivative PI‐PI.…”

Cucurbit[8]uril‐Based Polymers and Polymer Materials

“…Thus, although such guest‐guest interactions may exist, the interactions are often called “host–guest interactions” in general terms in the literature. In the following section, the driving forces of the polymerization of covalent monomers to fabricate linear or hyperbranched polymers will be roughly classified according to the original work into three types: a) HSCT interactions, b) host‐enhanced π–π interactions, and c) other host–guest interactions . There are virtually no pros and cons for different driving forces, as each designed monomer just applies to corresponding driving forces. a) HSCT Interactions …”

“…A linear supramolecular polymer was also constructed based on naphthalene‐modified α‐CD and CB[8] as hosts and the azobenzene‐bispyridinium conjugate as guest in an aqueous solution by the combination of the host–guest inclusion complex of α‐CD with trans‐azobenzene and the CB[8]‐stabilized CT complex between naphthalene and a bispyridinium salt . In another work of the same group, a heterowheel polypseudorotaxane was fabricated via self‐sorting supramolecular assembly by mixing naphthyl‐bridged bis(β‐CD), N,N ′‐dioctyl‐4,4′‐bipyridinium, CB[8], and 2,6‐dihydroxynaphthalene b) Host‐Enhanced π–π Interaction …”

Spatiotemporal control over the co-conformational switching in pH-responsive flavylium-based multistate pseudorotaxanes

“…[15][16][17][18] With respect to the molecular axles employed to devise CB-based rotaxanes and pseudorotaxanes, those containing viologen recognition units are by far the most frequently used because of the high stability constants of CB : viologen complexes and the redox switching properties of these molecules. [19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] The photochemical reduction of viologen units has also been explored in the presence of cucurbiturils to devise photoswitchable supramolecular assemblies. [35][36][37] In this work a molecular axle containing viologen and avylium units was synthesized and the formation of a pseudorotaxane with CB7 investigated (Scheme 1).…”