Macroscopic memory effects are exploited by various functional materials, such as self-tying surgical sutures and, most ubiquitously nowadays, liquid crystalline displays. These memory effects rely on the preservation of macroscopic or molecular structural information, respectively, from one state to another. Additional memory effects on intermediate length scales are expected to provide complex architectures with novel functions. A supramolecular orientational memory effect was recently discovered for two self-assembling dendrimers, one based on cyclotriveratrylene (CTV) and another based on perylene bisimide (PBI). These building blocks self-organize into columnar hexagonal arrays at low temperature. Upon heating, they transform into Pm3n cubic and body-centered cubic (Im3m) phases, respectively, both generated from supramolecular spheres. Upon cooling, the supramolecular spheres “remember” their orientations and generate columnar hexagonal domains oriented according to the directions of the preceding cubic phase. The resulting nanoscale architectures of CTV and PBI comprise orthogonally or tetrahedrally oriented columnar domains, respectively, and cannot be generated by any other means.

Supramolecular orientational memory: A new route to complex supramolecular architectures

254th National Meeting (2017)

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