Competing Interactions in Hierarchical Porphyrin Self-Assembly Introduce Robustness in Pathway Complexity.

Pathway complexity in supramolecular polymerization has recently sparked interest as a method to generate complex material behavior. The response of these systems relies on the existence of a metastable, kinetically trapped state. In this work, we show that strong switch-like behavior in supramolecular polymers can also be achieved through the introduction of competing aggregation pathways.

Supramolecular Organogels Formed through Complementary Double-Helix Formation.

Optically active amidine ((R)-1) and achiral carboxylic acid (2) dimers with a m-terphenyl backbone linked by a 1,4-phenylene diacetylene unit form a double helix, (R)-1⋅2, through complementary amidinium-carboxylate salt bridges in THF. Upon the addition of poor solvents, such as n-hexane, the duplex forms an organogel as a result of supramolecular polymerization of the duplex by intermolecular rearrangement of the salt bridges. In sharp contrast, an analogous racemic duplex composed of achiral amidine residues and an optically active duplex linked by a shorter diacetylene unit with a higher binding affinity than that of (R)-1⋅2 does not show any gelation.

Pulsating tubules from noncovalent macrocycles.

Despite recent advances in synthetic nanometer-scale tubular assembly, conferral of dynamic response characteristics to the tubules remains a challenge. Here, we report on supramolecular nanotubules that undergo a reversible contraction-expansion motion accompanied by an inversion of helical chirality. Bent-shaped aromatic amphiphiles self-assemble into hexameric macrocycles in aqueous solution, forming chiral tubules by spontaneous one-dimensional stacking with a mutual rotation in the same direction.

Optically active, amphiphilic poly(meta-phenylene ethynylene)s: synthesis, hydrogen-bonding enforced helix stability, and direct AFM observation of their helical structures.

Optically active, amphiphilic poly(meta-phenylene ethynylene)s (PPEa) bearing L- or D-alanine-derived oligo(ethylene glycol) side chains connected to the backbone via amide linkages were prepared by microwave-assisted polycondensation. PPEa's exhibited an intense Cotton effect in the π-conjugated main-chain chromophore regions in various polar and nonpolar organic solvents due to a predominantly one-handed helical conformation stabilized by an intramolecular hydrogen-bonding network between the amide groups of the pendants. The stable helical structure was retained in the bulk and led to supramolecular column formation from stacked helices in oriented polymer films as evidenced by X-ray diffraction.

Hierarchical amplification of macromolecular helicity of dynamic helical poly(phenylacetylene)s composed of chiral and achiral phenylacetylenes in dilute solution, liquid crystal, and two-dimensional crystal.

Optically active poly(phenylacetylene) copolymers consisting of optically active and achiral phenylacetylenes bearing L-alanine decyl esters (1L) and 2-aminoisobutylic acid decyl esters (Aib) as the pendant groups (poly(1L(m)-co-Aib(n))) with various compositions were synthesized by the copolymerization of the optically active 1L with achiral Aib using a rhodium catalyst, and their chiral amplification of the macromolecular helicity in a dilute solution, a lyotropic liquid crystalline (LC) state, and a two-dimensional (2D) crystal on the substrate was investigated by measuring the circular dichroism of the copolymers, mesoscopic cholesteric twist in the LC state (cholesteric helical pitch), and high-resolution atomic force microscopy (AFM) images of the self-assembled 2D helix-bundles of the copolymer chains. We found that the macromolecular helicity of poly(1L(m)-co-Aib(n))s could be hierarchically amplified in the order of the dilute solution, LC state, and 2D crystal. In sharp contrast, almost no chiral amplification of the macromolecular helicity was observed for the homopolymer mixtures of 1L and Aib in the LC state and 2D crystal on graphite.

Enantiomer-selective and helix-sense-selective living block copolymerization of isocyanide enantiomers initiated by single-handed helical poly(phenyl isocyanide)s.

Rigid-rodlike right (P)- and left (M)-handed helical polyisocyanides (P-poly-L-1 and M-poly-L-1) prepared by the living polymerization of an enantiomerically pure phenyl isocyanide bearing an L-alanine pendant with a long n-decyl chain (L-1) with the mu-ethynediyl Pt-Pd catalyst were found to block copolymerize L-1 and D-1 in a highly enantiomer-selective manner while maintaining narrow molecular weight distributions. The M-poly-L-1 preferentially copolymerized L-1 over the antipode D-1 by a factor of 6.4-7.