title: Chemical and constitutional influences in the self-assembly of functional supramolecular hydrogen-bonded nanoscopic fibres.
abstract: A new series of secondary amides bearing long alkyl chains with pi-electron-donor cores has been synthesized and characterised, and their self-assembly upon casting at surfaces has been studied. The different supramolecular assemblies of the materials have been visualized by using atomic force microscopy (AFM) and transmission electron microscopy (TEM). It is possible to obtain well-defined fibres of these aromatic core molecules as a result of the hydrogen bonds between the amide groups. Indeed, by altering the alkyl-chain lengths, constitutions, concentrations and solvent, it is possible to form different rodlike aggregates on graphite. Aggregate sizes with a lower limit of 6-8 nm width have been reached for different amide derivatives, while others show larger aggregates with rodlike morphologies which are several micrometers in length. For one compound that forms nanofibres, doping was performed by using a chemical oxidant, and the resulting layer on graphite was shown to exhibit metallic-like spectroscopy curves when probed with current-sensing AFM. This technique also revealed current maps of the surface of the molecular material. Fibre formation not only takes place on the graphite surface: nanometre scale rods have been imaged by using TEM on a grid after evaporation of solutions of the compounds in chloroform. Molecular modelling proves the importance of the hydrogen bonds in the generation of the fibres, and indicates that the constitution of the molecules is vital for the formation of the desired columnar stacks, results that are consistent with the images obtained by microscopic techniques. The results show the power of noncovalent bonds in self-assembly processes that can lead to electrically conducting nanoscale supramolecular wires.
authors.affiliation: Institut de Ciència de Materials de Barcelona (CSIC), Campus Universitari de Bellaterra, 08193 Cerdanyola del Vallès, Catalonia, Spain.
authors.forename: Josep
authors.initials: J
authors.lastname: Puigmartí-Luis
authors.forename: Andrea
authors.initials: A
authors.lastname: Minoia
authors.forename: Angel
authors.initials: A
authors.lastname: Pérez Del Pino
authors.forename: Gregori
authors.initials: G
authors.lastname: Ujaque
authors.forename: Concepció
authors.initials: C
authors.lastname: Rovira
authors.forename: Agustí
authors.initials: A
authors.lastname: Lledós
authors.forename: Roberto
authors.initials: R
authors.lastname: Lazzaroni
authors.forename: David B
authors.initials: DB
authors.lastname: Amabilino