No abstract

Unlike classical covalent polymers, one-dimensionally (1D) elongated supramolecular polymers (SPs) can be encoded with high degrees of internal order by the cooperative aggregation of molecular subunits, which endows these SPs with extraordinary properties and functions. However, this internal order has not yet been exploited to generate and dynamically control well-defined higher-order (secondary) conformations of the SP backbone, which may induce functionality that is comparable to protein folding/unfolding. Herein, we report light-induced conformational changes of SPs based on the 1D exotic stacking of hydrogen-bonded azobenzene hexamers. The stacking causes a unique internal order that leads to spontaneous curvature, which allows accessing conformations that range from randomly folded to helically folded coils. The reversible photoisomerization of the azobenzene moiety destroys or recovers the curvature of the main chain, which demonstrates external control over the SP conformation that may ultimately lead to biological functions.

Molecular recognition to preorganize noncovalently polymerizable supramolecular complexes is a characteristic process of natural supramolecular polymers, and such recognition processes allow for dynamic self-alteration, yielding complex polymer systems with extraordinarily high efficiency in their targeted function. We herein show an example of such molecular recognition-controlled kinetic assembly/disassembly processes within artificial supramolecular polymer systems using six-membered hydrogen-bonded supramolecular complexes (rosettes). Electron-rich and poor monomers are prepared that kinetically coassemble through a temperature-controlled protocol into amorphous coaggregates comprising a diverse mixture of rosettes. Over days, the electrostatic interaction between two monomers induces an integrative self-sorting of rosettes. While the electron-rich monomer inherently forms toroidal homopolymers, the additional electrostatic interaction that can also guide rosette association allows helicoidal growth of supramolecular copolymers that are comprised of an alternating array of two monomers. Upon heating, the helicoidal copolymers undergo a catastrophic transition into amorphous coaggregates via entropy-driven randomization of the monomers in the rosette.

Supramolecular polymers undergo self-folding on a time scale of days into topologies resembling the protein’s tertiary structures.

Hydrogen-bonded supermacrocycles (rosettes) are attractive disk-shaped noncovalent synthons for extended functional columnar nanoassemblies. They can serve not only as noncovalent monomer units for supramolecular polymers and discrete oligomers in a dilute solution but also as constituent entities for soft matters such as gels and lyotropic/thermotropic liquid crystals. However, what are the merits of using supramolecular rosettes instead of using expanded π-conjugated covalent molecules? This review covers the self-assembly of photochemically and electrochemically active π-conjugated molecules through the formation of supramolecular rosettes via directional complementary multiple hydrogen-bonding interactions. These rosettes comprising π-conjugated covalent functional units stack into columnar nanoassemblies with unique structures and properties. By overviewing the design principle, characterization, and properties and functionalities of various examples, we illustrate the merits of utilizing rosette motifs. Basically, one can easily access a well-defined expanded π-surface composed of multi-chromophoric systems, which can ultimately afford stable extended nanoassemblies even in a dilute solution due to the higher association constants of supermacrocyclized π-systems. Importantly, these columnar nanoassemblies exhibit unique features in self-assembly processes, chiroptical, photophysical and electrochemical properties, nanoscale morphologies, and bulk properties. Moreover, the stimuli responsiveness of individual building blocks can be amplified to a greater extent by exploiting rosette intermediates to organize them into one-dimensional columnar structures. In the latter parts of the review, we also highlight the application of rosettes in supramolecular polymer systems, photovoltaic devices, and others.