Journal
ACS NANO
Volume 10, Issue 11, Pages 10480-10488Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsnano.6b06419
Keywords
memory effect; complex arrangement; orthogonal columns; supramolecular; self-assembly
Categories
Funding
- National Science Foundation [DMR-1066116, DMR-1120901, OISE-1243313]
- Humboldt Foundation
- P. Roy Vagelos Chair at Penn
- joint NSF-EPSRC PIKE project RENEW' (EPSRC) [EP-K034308]
- Howard Hughes Medical Institute
- Division Of Materials Research
- Direct For Mathematical & Physical Scien [1066116] Funding Source: National Science Foundation
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Memory effects, including shape, chirality, and liquid-crystallinity, have enabled macroscopic materials with novel functions. However, the generation of complex supramolecular nanosystems via memory effects has not yet been investigated. Here, we report a cyclotriveratrylene-crown (CTV) compound that self-assembles into supra molecular columns and spheres forming, respectively, hexagonal and cubic mesophases. Upon transition from one phase to the other, an epitaxial relationship holds, via an unprecedented supramolecular orientational memory effect. Specifically, the molecular orientation and columnar character of supramolecular packing is preserved in the cubic phase, providing an otherwise inaccessible structure comprising orthogonally oriented domains of supramolecular columns. The continuous columnar character of tetrahedrally distorted supramolecular spheres self-organized from the CTV derivative in the faces of the Pm (3) over barn lattice is the basis of this supramolecular orientational memory, which holds throughout cycling in temperature between the two phases. This concept is expected to be general for other combinations of periodic and quasiperiodic arrays generated from supramolecular spheres upon transition to supramolecular columns.
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