title: Tetrahedral Arrangements of Perylene Bisimide Columns via Supramolecular Orientational Memory.
abstract: Chiral, shape, and liquid crystalline memory effects are well-known to produce commercial macroscopic materials with important applications as springs, sensors, displays, and memory devices. A supramolecular orientational memory effect that provides complex nanoscale arrangements was only recently reported. This supramolecular orientational memory was demonstrated to preserve the molecular orientation and packing within supramolecular units of a self-assembling cyclotriveratrylene crown at the nanoscale upon transition between its columnar hexagonal and Pm3̅n cubic periodic arrays. Here we report the discovery of supramolecular orientational memory in a dendronized perylene bisimide (G2-PBI) that self-assembles into tetrameric crowns and subsequently self-organizes into supramolecular columns and spheres. This supramolecular orientation memory upon transition between columnar hexagonal and body-centered cubic (BCC) mesophases preserves the 3-fold cubic [111] orientations rather than the 4-fold [100] axes, generating an unusual tetrahedral arrangement of supramolecular columns. These results indicate that the supramolecular orientational memory concept may be general for periodic arrays of self-assembling dendrons and dendrimers as well as for other periodic and quasiperiodic nanoscale organizations comprising supramolecular spheres, generated from other organized complex soft matter including block copolymers and surfactants.
authors.affiliation: Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Dipankar
authors.initials: D
authors.lastname: Sahoo
authors.affiliation: Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.|Department of Physics and Astronomy, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6396, United States.
authors.forename: Mihai
authors.identifier: 0000-0002-7247-4008
authors.initials: M
authors.lastname: Peterca
authors.affiliation: Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Emad
authors.initials: E
authors.lastname: Aqad
authors.affiliation: Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Benjamin E
authors.identifier: 0000-0003-2359-1280
authors.initials: BE
authors.lastname: Partridge
authors.affiliation: Department of Physics and Astronomy, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6396, United States.
authors.forename: Paul A
authors.initials: PA
authors.lastname: Heiney
authors.affiliation: Max-Planck Institute for Polymer Research , Mainz 55128, Germany.
authors.forename: Robert
authors.initials: R
authors.lastname: Graf
authors.affiliation: Max-Planck Institute for Polymer Research , Mainz 55128, Germany.
authors.forename: Hans W
authors.initials: HW
authors.lastname: Spiess
authors.affiliation: Department of Materials Science and Engineering, University of Sheffield , Sheffield S1 3JD, United Kingdom.
authors.forename: Xiangbing
authors.initials: X
authors.lastname: Zeng
authors.affiliation: Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Virgil
authors.identifier: 0000-0001-5926-0489
authors.initials: V
authors.lastname: Percec
keywords: body-centered cubic; oriented columns; perylene bisimide spheres; self-assembly; supramolecular orientational memory; tetrahedral