Hydrogen-bonded rosettes comprising π-conjugated systems as building blocks for functional one-dimensional assemblies

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 pi-conjugated covalent molecules? This review covers the self-assembly of photochemically and electrochemically active pi-conjugated molecules through the formation of supramolecular rosettes via directional complementary multiple hydrogen-bonding interactions. These rosettes comprising pi-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 pi-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 pi-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.