Narrow-energy gap conjugated polymers based on benzobisthiadiazole and thiadiazoloquinoxaline: DFT and TDDFT study

Herein, the HOMO-LUMO energy gaps (Eg) and UV spectra of benzo[1,2-c:4,5-c']bis([1,2,5]thiadiazole (BBT) and [1,2,5]thiadiazolo[3,4-g]quinoxaline (TQ)-based donor-acceptor-donor type-conjugated polymers were computed by using density functional theory (DFT) and time-dependent density functional theory (TD-DFT) at B3LYP/6-31G(d,p) level. The donor groups consist of thiophene (TH), 3,4-ethylenedioxythiophene (EDOT), and 3,4-propylene dioxythiophene (ProDOT) units and the bisthiadiazole and thiadiazoloquinoxaline were chosen as electron acceptor groups. To examine the effects of the alkyl side chain on the molecular structure and Eg of the polymer, methyl groups were added at the 3,4-, 2,3-, and 3,3-positions of TH, EDOT, and ProDOT donor groups, respectively. Our calculated HOMO-LUMO energy gaps are in the range of 0.05 to 1.37 eV. The calculation results show that the energy gaps are in line with the available experimental values. The novel BBT and TQ derivatives with improved optical and electronic properties may find use in electronic applications. Graphical abstract.