Supramolecular Polymer Polymorphism: Spontaneous Helix-Helicoid Transition through Dislocation of Hydrogen-Bonded π-Rosettes.

Polymorphism, a phenomenon whereby disparate self-assembled products can be formed from identical molecules, has incited interest in the field of supramolecular polymers. Conventionally, the monomers that constitute supramolecular polymers are engineered to facilitate one-dimensional aggregation and, consequently, their polymorphism surfaces primarily when the states of assembly differ significantly. This engenders polymorphs of divergent dimensionalities such as one- and two-dimensional aggregates. Notwithstanding, realizing supramolecular polymer polymorphism, wherein polymorphs maintain one-dimensional aggregation, persists as a daunting challenge. In this work, we expound upon the manifestation of two supramolecular polymer polymorphs formed from a large discotic supramolecular monomer (rosette), which consists of six hydrogen-bonded molecules with an extended π-conjugated core. These polymorphs are generated in mixtures of chloroform and methylcyclohexane, attributable to distinctly different disc stacking arrangements. The face-to-face (minimal displacement) and offset (large displacement) stacking arrangements can be predicated on their distinctive photophysical properties. The face-to-face stacking results in a twisted helix structure. Conversely, the offset stacking induces inherent curvature in the supramolecular fiber, thereby culminating in a hollow helical coil (helicoid). While both polymorphs exhibit bistability in nonpolar solvent compositions, the face-to-face stacking attains stability purely in a kinetic sense within a polar solvent composition and undergoes conversion into offset stacking through a dislocation of stacked rosettes. This occurs without the dissociation and nucleation of monomers, leading to unprecedented helicoidal folding of supramolecular polymers. Our findings augment our understanding of supramolecular polymer polymorphism, but they also highlight a distinctive method for achieving helicoidal folding in supramolecular polymers.

Effect of an Aromatic Solvent on Hydrogen-Bond-Directed Supramolecular Polymerization Leading to Distinct Topologies.

Beyond phenomenon, self-assembly of synthetic molecules, is now becoming an essential tool to design supramolecular materials not only in the thermodynamically stable state but also in kinetically trapped states. However, an approach to design complex self-assembly processes comprising different types of self-assembled states remains elusive. Herein, an example of such systems is demonstrated based on a unique supramolecular polymer mediated by supermacrocyclization of hydrogen-bonding π-conjugated molecules. By adding an aromatic solvent into nonpolar solutions of the monomer, spontaneous nucleation triggered by supermacrocyclization was suppressed so that isothermal supramolecular polymerization could be achieved from kinetically formed topological variants and amorphous agglomerates to afford helicoidal structures hitherto obtainable only with very slow cooling of a hot solution. By increasing the proportion of aromatic solvent further, another self-assembly path was found, based on competing extended hydrogen-bonded motifs affording crystalline nanowires.

Triplet-Triplet Annihilation-Based Upconversion Sensitized by a Reverse Micellar Assembly of Amphiphilic Ruthenium Complexes.

We have developed a new photon upconversion (UC) system utilizing a new amphiphilic sensitizer 1a that comprises a hydrophilic ruthenium complex and a lipophilic bisanthracene appendage. At concentrations higher than 5 µM in toluene, the sensitizer 1a formed a reverse micellar assembly which facilitated the triplet sensitization of 9,10-diphenylanthracene (DPA) more efficiently than homogeneously dispersed solutions to enhance the UC efficiency up to 38.2%. The Stern-Volmer analyses revealed the stepwise triplet-triplet energy transfers (TTET): (1) intramicellar energy transfer from the ruthenium core to the bisanthracene surface and (2) diffusion-dependent energy transfer from the surface to DPA. On these bases, it can be assumed that the reverse micellar assemblies accelerate the former TTET process to enhance the UC efficiency.

Fluorescent supramolecular polymers of barbiturate dyes with thiophene-cored twisted π-systems.

Because supramolecular polymerization of emissive π-conjugated molecules depends strongly on π-π stacking interaction, the formation of well-defined one-dimensional nanostructures often results in a decrease or only a small increase of emission efficiency. This is also true for our barbiturate-based supramolecular polymers wherein hydrogen-bonded rosettes of barbiturates stack quasi-one-dimensionally through π-π stacking interaction. Herein we report supramolecular polymerization-induced emission of two regioisomeric 2,3-diphenylthiophene derivatives functionalized with barbituric acid and tri(dodecyloxy)benzyl wedge units. In CHCl3, both compounds are molecularly dissolved and accordingly poorly emissive due to a torsion-induced non-radiative decay. In methylcyclohexane-rich conditions, these barbiturates self-assemble to form crystalline nanofibers and exhibit strongly enhanced emission through supramolecular polymerization driven by hydrogen-bonding. Our structural analysis suggests that the barbiturates form a tape-like hydrogen-bonding motif, which is rationalized by considering that the twisted geometries of 2,3-diphenylthiophene cores prevend the competing rosettes from stacking into columnar supramolecular polymers. We also found that a small difference in the molecular polarity originating from the substitutional position of the thiophene core influences interchain association of the supramolecular polymers, affording different luminescent soft materials, gel and nanosheet.

Supramolecular polymerization of thiobarbituric acid naphthalene dye.

2-Thiobarbituric acid-functionalized naphthalene dye selectively self-assembles into crystalline fibers to show material properties that are different from those of a previously reported oxo-barbituric acid derivative affording curved supramolecular polymers via the formation of hydrogen-bonded rosettes. Detailed studies using 1H-NMR, DFT calculation and X-ray diffraction revealed that the crystalline fiber is formed through a tape-like hydrogen-bonding pattern due to the weaker hydrogen-bond-acceptor ability of the thiocarbonyl group.

Wavy supramolecular polymers formed by hydrogen-bonded rosettes.

A barbiturate-functionalized supramolecular monomer bearing an ester-linked biphenyl and azobenzene π-conjugated core affords wavy supramolecular polymers. The periodic inversion of curvature is due to the conformational rigidity of the monomer and repulsive interactions between rosettes. Photoisomerization of the azobenzene moiety increases the fragility of the main chain without deteriorating its periodic structure.

Hydrogen bond-directed supramolecular polymorphism leading to soft and hard molecular ordering.

Transformation of metastable supramolecular stacks of hydrogen-bonded rosettes composed of an ester-containing barbiturated naphthalene into crystalline nanosheets occurs through the rearrangement of hydrogen-bonding patterns. The involvement of the ester group in the crystalline hydrogen-bonded pattern is demonstrated, guiding us to a new molecular design that can afford supramolecular polymorphs with soft and hard molecular packing.