Rapid Syntheses of Oligo(2,5-thiophene ethynylene)s with Thioester Termini: Potential Molecular Scale Wires with Alligator Clips

Abstract

The syntheses of soluble oligo(3-ethyl-2,5-thiophene ethynylene)s via an iterative divergent/convergent approach starting from 3-ethyl-2-(trimethylsilylethynyl)thiophene are described. The monomer, dimer, tetramer, octamer, and 16-mer were synthesized. The 16-mer is 100 Å long in its minimized extended zigzag conformation. At each stage in the iteration, the length of the framework doubles. Only three sets of reaction conditions are needed for the entire iterative synthetic sequence: an iodination, a protodesilylation, and a Pd/Cu-catalyzed cross coupling. The oligomers were characterized spectroscopically and by mass spectrometry. The optical properties are presented which show that at the octamer stage, the optical absorbance maximum is nearly saturated. The size exclusion chromatography values for the number average weights, relative to polystyrene, illustrate the tremendous differences in the hydrodynamic volume of these rigid rod oligomers verses the random coils of polystyrene. These differences become quite apparent at the octamer stage. Attachment of thiol end groups, protected as the thioacetyl moieties, was achieved. These serve as binding sites for adhesion to gold surfaces. In some cases, one end of the oligomeric chains were capped with a thiol group so that the surface attachments to gold could be studied. In other cases, thiol groups were affixed to both ends of the molecular chains so that future conduction studies could be done between proximal metallic probes. The rigid rod conjugated oligomers may act as molecular wires in molecular scale electronic devices, and they also serve as useful models for understanding analogous bulk polymers.