Self-repairing complex helical columns generated via kinetically controlled self-assembly of dendronized perylene...

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.