Photophysics and charge transfer in oligo(thiophene) based conjugated diblock oligomers

This paper reports an investigation of the electronic structure and photophysical properties of two "diblock" π-conjugated oligomers (T4-TBT and T8-TBT) that feature electron rich tetra(thiophene) (T4) or octa(thiophene) (T8) segments linked to an electron poor 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole (TBT) moiety. Electrochemistry and UV-visible absorption spectroscopy reveals that the diblock oligomers display redox and absorption features that can be attributed to the Tn and TBT units. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations support the experimental electrochemistry and optical spectroscopy results, suggesting that the frontier orbitals on the diblock oligomers retain characteristics of the individual π-conjugated segments. However, low energy optical transitions are anticipated to arise from Tn to TBT charge transfer. Fluorescence spectroscopy on the diblock oligomers reveals that the oligomers feature strongly solvent dependent fluorescence. In non-polar solvents (hexane, toluene), the emission is structured with a moderate Stokes shift; however, in more polar solvents the emission becomes broader, and red-shifts significantly. Transient absorption spectroscopy on timescales from femtoseconds (fs) to microseconds (μs) reveals that in non-polar solvents excitation produces a singlet excited state (LE) that decays uniformly to the ground state in parallel with intersystem crossing to a triplet state. By contrast, in more polar solvents, excitation produces a very short-lived excited state (1-3 ps) which evolves rapidly into a second excited state that is attributed to the charge transfer (CT) state. The fast dynamics are associated with crossing from the LE state, which is populated initially by photoexcitation, into the CT state, which then decays to the ground state. The photophysical properties and dynamics of the LE and CT excited states are very similar for T4-TBT and T8-TBT, suggesting that the length of the oligo(thiophene) segment does not have a strong influence on the energy, structure or dynamics of the LE and CT excited states.