Monolayers and multilayers of conjugated polymers as nanosized electronic components

Conjugated polymers (CPS) are interesting materials for preparing devices based on nanoscopic molecular architectures because they exhibit electrical, electronic, magnetic, and optical properties similar to those of metals or semiconductors while maintaining the flexibility and ease of processing of polymers. The production of well-defined mono- and multilayers of CPS on electrodes with nanometer-scale, one-dimensional resolution remains, however, an important challenge. In this Account, we describe the preparation and conductive properties of nanometer-sized CP molecular struc tures formed on electrode surfaces-namely, self-assembled monolayer (SAM), brush-type, and self-assembled multilayer CPs-and in combination with gold nanoparticles (AuNPs). We have electrochemically polymerized SAMs of carboxy- alkyl-functionalized terthiophenes aligned either perpendic- ular or parallel to the electrode surface. Anodic coupling of various pyrrole- and thiophene-based monomers in solu tion with the oligothiophene-based SAMS produced brushlike films. Microcontact printing of these SAMs produced patterns that, after heterocoupling, exhibited large height enhancements, as measured using atomic force microscopy (AFM). We have employed layer-by-layer self-assembly of water-soluble polythiophene-based polyelectrolytes to form self-assembled multilayers. The combination of isostructural polycationic and polyanionic polythiophenes produced layers of chains aligned parallel to the substrate plane. These stable, robust, and dense layers formed with high regularity on the preformed monolayers, with minimal interchain penetration. Infrared reflection/adsorption spectroscopy and X-ray diffraction analyses revealed unprecedented degrees of order. Deposition of soluble polypyrroles produced molecular layers that, when analyzed using a goldcoated AFM tip, formed gold - polymer-gold junctions that were either ohmic or rectifying, depending of the layer sequence. We also describe the electronic conduction of model alpha,omega-capped sexithlophenes featuring a range of electron donor/acceptor units and lengths of additional conjugation. The sexithiophene cores exhibit redox-type conductivity, developing at the neutral/cation and cation/dication levels with values depending the nature of the substitution and the redox system. Extending the conjugation beyond the sexithiophene frame introduces further oxidation processes displaying enhanced conductivity. Finally, we discuss the ability of CP-based monolayers to coordinate AuNPs. Although thiophene- and pyrrole-based oligomers aggregate toluene-soluble AuNPs, alkyl substitution inhibits the aggregation process through steric restraint. Consequently, we investigated the interactions between AuNFs and polypyrrole or polythiophene monolayers, including those formed from star-shaped molecules. The hindered aggregation provided by alkyl substituents allowed us to adsorb thiol-functionalized oligothiophenes and oligopyrroles directly onto preformed AuNFs. Novel materials incorporating AuNPs of the same size but bearing different conjugated ends or bridges have great promise for applications in electrocatalysis, electroanalysis, and organic electronics.