Conductive, magnetic, and optical properties of sterically hindered dodecithiophenes. evidence for the coexistence of bipolaron and π-dimer

Conductive, magnetic, and optical properties of sterically hindered dodecithiophenes bearing bulky 2,2-bis(butoxy-methyl)-l,3-propanediyl groups were examined. At high doping with FeCl₃, a completely hindered dodecithiophene had only a poor conductivity of 5 × 10^-4 S cm^-1, but two partially hindered dodecithiophenes had relatively high conductivities of 1.9 and 0.6 S cm^-1, which are one or two orders lower than the conductivity (38 S cm^-1) of the unhindered odecithiophene. Despite having different structures and conductivities, all of the doped solids of these dodecithiophenes were magnetically inactive and demonstrated similar optical absorption spectra in the near infrared region, as generally observed for polythiophenes. On the other hand, their optical spectra in dichloromethane were quite different from one another. A solution spectrum of the unhindered dodecithiophene under high doping was characterized by two absorption transitions assignable to a π-dimer. On the other hand, a solution spectrum of the completely hindered dodecithiophene was characterized by an absorption transition due to a bipolaron. Furthermore, the solution spectra of two partially hindered dodecithiophenes could be explained as an overlap of both π-dimeric and bipolaronic bands. From these results, both π-dimer and bipolaron species appear to serve as active charge carriers in conductive poly(oligo)thiophenes.