Self‐Organization and Charge Transport Properties of Selenium and Tellurium Analogues of Polythiophene

A series of conjugated polymers comprising polythiophene, polyselenophene, and polytellurophene with branched 3,7‐dimethyloctyl side chains, well‐matched molecular weight, dispersity, and regioregularity is synthesized. The ionization potential is found to vary from 5.14 to 5.32 eV, with polytellurophene having the lowest potential. Field‐effect transistors based on these materials exhibit distinct hole transport mobility that varies by nearly three orders of magnitude, with polytellurophene having the highest mobility (2.5 × 10−2 cm² V−1 s−1). The large difference in mobility demonstrates the significant impact of heteroatom substitution. Although the series of polymers are very similar in structure, their solid‐state properties are different. While the thin film microstructure of polythiophene and polyselenophene is identical, polytellurophene reveals globular features in the film topography. Polytellurophenes also appear to be the least crystalline, even though their charge transport properties are superior to other samples. The torsional barrier and degree of planarity between repeat units increase as one moves down group‐16 elements. These studies show how a single atom in a polymer chain can have a substantial influence on the bulk properties of a material, and that heavy group‐16 atoms have a positive influence on charge transport properties when all other variables are kept unchanged. Polythiophene, polyselenophene, and polytellurophene with an identical side chain are prepared with well‐matched molecular weight, dispersity, and regioregularity. One single atom change in a polymer chain is shown to have a substantial impact on the properties of these materials. Polytellurophene appears to be the least crystalline but exhibits the highest mobility in field‐effect transistors.