Over the past decade, major progress in supramolecular polymerization has had a substantial effect on the design of functional soft materials. However, despite recent advances, most studies are still based on a preconceived notion that supramolecular polymerization follows a step-growth mechanism, which precludes control over chain length, sequence, and stereochemical structure. Here we report the realization of chain-growth polymerization by designing metastable monomers with a shape-promoted intramolecular hydrogen-bonding network. The monomers are conformationally restricted from spontaneous polymerization at ambient temperatures but begin to polymerize with characteristics typical of a living mechanism upon mixing with tailored initiators. The chain growth occurs stereoselectively and therefore enables optical resolution of a racemic monomer.
A new approach toward higher efficiency organic photovoltaic devices (OPVs) is described. Complementarity in shape between the donor (contorted hexabenzocoronene, see picture) and acceptor (buckminsterfullerene) molecules results in OPVs that perform surprisingly well. This exploitation of host–guest chemistry at the organic/organic interface demonstrates a new direction for OPV device design.
Ultrafast water permeation in aquaporins is promoted by their hydrophobic interior surface. Polytetrafluoroethylene has a dense fluorine surface, leading to its strong water repellence. We report a series of fluorous oligoamide nanorings with interior diameters ranging from 0.9 to 1.9 nanometers. These nanorings undergo supramolecular polymerization in phospholipid bilayer membranes to form fluorous nanochannels, the interior walls of which are densely covered with fluorine atoms. The nanochannel with the smallest diameter exhibits a water permeation flux that is two orders of magnitude greater than those of aquaporins and carbon nanotubes. The proposed nanochannel exhibits negligible chloride ion (Cl
–
) permeability caused by a powerful electrostatic barrier provided by the electrostatically negative fluorous interior surface. Thus, this nanochannel is expected to show nearly perfect salt reflectance for desalination.
For the concept of aromaticity, energetic quantification is crucial. However, this has been elusive for excited-state (Baird) aromaticity. Here we report our serendipitous discovery of two nonplanar thiophene-fused chiral [4n]annulenes Th4
COT
Saddle and Th6
CDH
Screw, which by computational analysis turned out to be a pair of molecules suitable for energetic quantification of Baird aromaticity. Their enantiomers were separable chromatographically but racemized thermally, enabling investigation of the ring inversion kinetics. In contrast to Th6
CDH
Screw, which inverts through a nonplanar transition state, the inversion of Th4
COT
Saddle, progressing through a planar transition state, was remarkably accelerated upon photoexcitation. As predicted by Baird’s theory, the planar conformation of Th4
COT
Saddle is stabilized in the photoexcited state, thereby enabling lower activation enthalpy than that in the ground state. The lowering of the activation enthalpy, i.e., the energetic impact of excited-state aromaticity, was quantified experimentally to be as high as 21–22 kcal mol–1.
Although mechanically robust polymer
materials had not been thought
to self-heal, we recently found that poly(ether thiourea) PTUEG3, which is a glassy polymer with high mechanical strength,
self-heals even at ambient temperatures. This finding updated the
above preconception. Nevertheless, it should also be noted that PTUEG3, under high humidity, absorbs water and is plasticized to
lose its mechanical strength. Humidity-induced plasticization is a
general problem for polymers with polar groups. Herein, we report
that PTUEG3, if designed by copolymerization to contain
only 10 mol % of a dicyclohexylmethane (Cy2M) thiourea
unit (TUCy2M), serves as a humidity-tolerant, mechanically
robust polymer material that can self-heal at ambient temperatures.
This copolymer contained, in its ether thiourea (TUEG3)-rich
domain, a humidity-tolerant, noncovalently cross-linked 3D network
with mechanical robustness formed by stacking of the Cy2M group. The present work provides a promising design strategy for
mechanically robust, self-healable polymers usable under high humidity.
Disk- and rod-shaped molecules are incompatible in coassembly, as the former tend to stack one-dimensionally whereas the latter tend to align in parallel. Because this type of incompatibility can be more pronounced in condensed phases, different-shaped molecules generally exclude one another. We report that supramolecular polymerization of a disk-shaped chiral monomer in nematic liquid crystals comprising rod-shaped molecules results in order-increasing mesophase transition into a single mesophase with a core-shell columnar geometry. This liquid crystalline material responds quickly to an applied electric field, resulting in unidirectional columnar ordering. Moreover, it can be modularly customized to be optoelectrically responsive simply by using a photoisomerizable rod-shaped module. The modular strategy allows for cooperative integration of different functions into elaborate dynamic architectures.
Being inspired by naturally occurring peptidic macrocycles, we developed liquid-crystalline (LC) compounds 1 and 2 that are capable of self-assembling into hexagonal columnar mesophases over a wide temperature range that includes room temperature. Their bowl-shaped macrocyclic cores are conformationally robust because of the presence of internal H-bonds, while the columnar assembly is ensured by intermolecular H-bonding interactions involving the exocyclic amide units. When an electric field was applied to their LC films from a direction orthogonal to the film plane, the columns were oriented homeotropically over a large area.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.