title: Self-repairing complex helical columns generated via kinetically controlled self-assembly of dendronized perylene bisimides.
abstract: The dendronized perylene 3,4:9,10-tetracarboxylic acid bisimide (PBI), (3,4,5)12G1-3-PBI, was recently reported to self-assemble in complex helical columns containing tetramers of PBI as basic repeat unit. These tetramers contain a pair of two molecules arranged side-by-side and another pair in the next stratum of the column turned upside-down and rotated around the column axis. Intra- and intertetramer rotation angles and stacking distances are different. At high temperature, (3,4,5)12G1-3-PBI self-assembles via a thermodynamically controlled process in a 2D hexagonal columnar phase while at low temperature in a 3D orthorhombic columnar array via a kinetically controlled process. Here, we report the synthesis and structural analysis, by a combination of differential scanning calorimetry, X-ray and electron diffraction, and solid-state NMR performed at different temperatures, on the supramolecular structures generated by a library of (3,4,5)nG1-3-PBI with n = 14-4. For n = 11-8, the kinetically controlled self-assembly from low temperature changes in a thermodynamically controlled process, while the orthorhombic columnar array for n = 9 and 8 transforms from the thermodynamic product into the kinetic product. The new thermodynamic product at low temperature for n = 9, 8 is a self-repaired helical column with an intra- and intertetramer distance of 3.5 Å forming a 3D monoclinic periodic array via a kinetically controlled self-assembly process. The complex dynamic process leading to this reorganization was elucidated by solid-state NMR and X-ray diffraction. This discovery is important for the field of self-assembly and for the molecular design of supramolecular electronics and solar cell.
authors.affiliation: Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, United States. percec@sas.upenn.edu
authors.forename: Virgil
authors.initials: V
authors.lastname: Percec
authors.forename: Steven D
authors.initials: SD
authors.lastname: Hudson
authors.forename: Mihai
authors.initials: M
authors.lastname: Peterca
authors.forename: Pawaret
authors.initials: P
authors.lastname: Leowanawat
authors.forename: Emad
authors.initials: E
authors.lastname: Aqad
authors.forename: Robert
authors.initials: R
authors.lastname: Graf
authors.forename: Hans W
authors.initials: HW
authors.lastname: Spiess
authors.forename: Xiangbing
authors.initials: X
authors.lastname: Zeng
authors.forename: Goran
authors.initials: G
authors.lastname: Ungar
authors.forename: Paul A
authors.initials: PA
authors.lastname: Heiney
mesh_terms: D050091:Dendrimers / Q000138:chemical synthesis* / Q000737:chemistry; D007094:Imides / Q000138:chemical synthesis* / Q000737:chemistry; D007700:Kinetics; D015394:Molecular Structure; D010569:Perylene / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry
chemical_list: D050091:Dendrimers; D007094:Imides; C510697:perylene bisimide; D010569:Perylene