Self-Repairing Complex Helical Columns Generated via Kinetically Controlled Self-Assembly of Dendronized Perylene Bisimides

Published

November 16, 2011

Author(s)

Virgil Percec, Steven Hudson, Mihai Peterca, Pawaret Leowanawat, Emad Aqad, Robert Graf, Hans -. Spiess, Xiangbing Zeng, Goran Ungar, Paul A. Heiney

Abstract

The dendronized perylene 3,4:9,10-tetracarboxylic acid bisimide (PBI) (3,4,5)12G1-3-PBI was recently shown to self-assemble in a complex helical column containing tetramers of PBI as the basic repeat unit. The 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. The intra- and inter-tetramer rotation angle and stacking distance are different. At high temperature this dendronized PBI self-assemble 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 of a library of (3,4,5)nG1-3-PBI with n = 14 to 4, and the discovery that at n = 9 and 8 the kinetically controlled self-assembly from low temperature is transformed in a thermodynamically controlled process. In addition, the orthorhombic columnar array for n = 9 and 8 transforms from the thermodynamic product into kinetic one. The new thermodynamic product at low temperature is a self-repaired helical column with identical intra- and inter-tetramer distance of 3.5 Å that forms a 3D monoclinic periodic array via a kinetically controlled self-assembly process. This remarkable discovery is important for both the fundamental understanding of the self-assembly and for technological applications related to the molecular design of supramolecular electronics and solar cell.

Citation

Journal of the American Chemical Society

Volume

133

Issue

45

Pub Type

Journals

Keywords

self assembly, diffraction, organic electronics, photovoltaics

Citation

Percec, V. , Hudson, S. , Peterca, M. , Leowanawat, P. , Aqad, E. , Graf, R. , Spiess, H. , Zeng, X. , Ungar, G. and Heiney, P. (2011), Self-Repairing Complex Helical Columns Generated via Kinetically Controlled Self-Assembly of Dendronized Perylene Bisimides, Journal of the American Chemical Society (Accessed October 13, 2024)