The discovery of electrically conducting organic crystals and polymers has widened the range of potential optoelectronic materials, provided these exhibit sufficiently high charge carrier mobilities and are easy to make and process. Organic single crystals have high charge carrier mobilities but are usually impractical, whereas polymers have good processability but low mobilities. Liquid crystals exhibit mobilities approaching those of single crystals and are suitable for applications, but demanding fabrication and processing methods limit their use. Here we show that the self-assembly of fluorinated tapered dendrons can drive the formation of supramolecular liquid crystals with promising optoelectronic properties from a wide range of organic materials. We find that attaching conducting organic donor or acceptor groups to the apex of the dendrons leads to supramolecular nanometre-scale columns that contain in their cores pi-stacks of donors, acceptors or donor-acceptor complexes exhibiting high charge carrier mobilities. When we use functionalized dendrons and amorphous polymers carrying compatible side groups, these co-assemble so that the polymer is incorporated in the centre of the columns through donor-acceptor interactions and exhibits enhanced charge carrier mobilities. We anticipate that this simple and versatile strategy for producing conductive pi-stacks of aromatic groups, surrounded by helical dendrons, will lead to a new class of supramolecular materials suitable for electronic and optoelectronic applications.

The structure and the associated dynamics have been investigated in a series of oligopeptides of gamma-benzyl-l-glutamate using DSC, WAXS, FTIR, NMR and dielectric spectroscopy, and rheology, respectively. The peptides with degrees of polymerization below 18 are mixtures of a lamellar assembly of beta sheets and of columnar hexagonal arrangement of alpha helices, whereas for longer chains, the intramolecular hydrogen bonds stabilize only the alpha-helical conformations. Multiple dielectrically active processes were found. Starting from low temperatures, the two Arrhenius processes (gamma and beta), with apparent activation energies of 20.6 and 50.2 kJ/mol, respectively, associate with the local relaxation of the side-chain methylene units (gamma process) and with more cooperative motions of the side chain dipoles sensitive to the 7/2 helical packing (beta process). The glass transition is manifested in the thermal properties with a step in the heat capacity and with an intense dielectric process bearing characteristics (molecular weight dependence, temperature dependence of relaxation times) known from amorphous polymers. Based on these findings, the alpha process is attributed to the relaxation of amorphous segments located between and at the end of helically ordered segments. Two slower processes were identified with opposite molecular weight dependence. The weak intermediate mode with an M2 molecular weight dependence of the characteristic relaxation times suggests amorphous-like chains, whereas the strong slower process originates from the loss of dipole orientational capacity caused by structural defects and reflects the migration of helical sequences along the chains. This identifies the helices as structures extending over rather short fragments of chains (i.e., of low persistence length). The viscoelastic response indicated that the structural defects arise from locally aggregated chains that inhibit the flow of oligopeptides.

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