Concentration-dependent supramolecular self-assembly of A1/A2-asymmetric-difunctionalized pillar[5]arene

Abstract

Concentration-dependent supramolecular self-assembly of A1/A2-asymmetric-difunctionalized pillar[5]arene was synthesized by co-cyclization strategy. This approach enables wide range of structural manipulations to regulate the supramolecular assembly.

Noncovalently bound and mechanically interlocked systems using pillar[n]arenes

“…110 In P63b , dimer formation was supported by a very low specific viscosity and its linear correlation with concentration. Similar dimeric assemblies were observed for an benzyl-substituted molecule ( P63c ), 157 and some self-inclusion molecules described above in the crystalline state ( P31a in Scheme 10) 122 and under concentrated conditions ( P36 in Fig. 19).…”

Spatially Designed Supramolecular Anion Receptors Based on Pillar[5]arene Scaffolds: Synthesis and Halide Anion Binding Properties

“…The diffusion-ordered spectroscopy (DOSY) technique has been successively employed to characterize host−guest complexation behaviors and various types of supramolecular assemblies by correlation of 1 H NMR signals with the diffusion coefficient (D) in solution. 33,34 Thus, the host−guest complexation behavior of compound 1,3-BUP with fluoride (F − ) was studied by DOSY experiments. Interestingly, the DOSY Assuming all assemblies are hydrodynamically spherical, the number-average degree of aggregation of the "supramolecular assembly" can be estimated using the diffusion coefficient obtained from DOSY measurements according to the Stokes− Einstein equation [N ≈ 1/(D/D ref ) 3 ].…”

“…The diffusion-ordered spectroscopy (DOSY) technique has been successively employed to characterize host–guest complexation behaviors and various types of supramolecular assemblies by correlation of 1 H NMR signals with the diffusion coefficient ( D ) in solution. , Thus, the host–guest complexation behavior of compound 1,3-BUP with fluoride (F – ) was studied by DOSY experiments. Interestingly, the DOSY spectrum in DMSO- d 6 at 5 mM of the receptor 1,3-BUP with two equivalents of F – revealed three sets of signals, manifesting the presence of three different aggregate sizes in solution with measured the weight-average diffusion ( D ) of 9.83 × 10 –10 , 2.91 × 10 –10 , and 1.12 × 10 –10 m 2 s –1 (Figure ).…”

Pillar[5]arene-Derived endo-Functionalized Molecular Tube for Mimicking Protein–Ligand Interactions

“…Therefore, to imitate the microenvironment within protein binding pockets, the interior surface of the biomimetic receptors must possess polar functionalities for H-bond formation. To this end, there have been reports of pocket-shaped receptors, − such as cavitands, glucose receptor 2, aryl-extended calix[4]­pyrrole receptors, and helical aromatic and oligoamide foldamers (Figure a–e). , Jiang’s group recently made significant progress in transforming naphthalene-based tubular molecules into biomimetic tubes in which the inwardly directed functional groups improved their binding affinity and selectivity toward fragment ligands (Figure f). − As a class of tubular-shaped macrocyclic hosts, pillar­[ n ]­arenes − could seat various functional substituents on their rims, for instance, amino acids or short peptides, for mimicking transmembrane channels . Nonetheless, all of these rim-embedded polar functional substituents pointed outward, and there has been no report about the mounting polar functionalities pointing inward into the cavity cores of pillar­[ n ]­arenes.…”