The novel non-fully-fused ring small molecule acceptors: End-capped modification investigation

Abstract

End-capped modification is an efficacious strategy for developing high-performance acceptor materials. In this paper, the experimentally synthesized A-D-A'-D-A type non-fully-fused ring acceptor IDTBT-4F (R) was used as a reference molecule, and five small molecule acceptors for R1-R5 were investigated by changing R's terminal functional groups. By using DFT/B3PW91/6-31G (d,p) method, the ground-state structures of all molecules were studied. The absorption spectra of these acceptors were gained by the TD-DFT/MPW1PW91/6-31G (d,p) approach. Meanwhile, the charge density difference and transition density matrix were analyzed effectively. It can be observed that, compared to the R molecule, all developed molecules exhibited narrower energy gaps, larger absorption wavelengths, more red-shifted absorption spectra, lower excitation energies, higher dipole moment and greater electron-accepting capacity. The strategy of functional group substitution is superior to halogen substitution in improving the aforementioned parameters. Both terminal π-extension and end-group chlorination strategies can synergistically enhance molecular performance. In addition, we also calculated the electron mobility of the dimers constructed by all the molecules, among which R1 and R4 molecules designed with -COOCH₃ functional group substitution and R2 molecule with terminal chlorination achieved superior electron mobility compared to R molecule due to their significant electronic coupling. Overall, the study shows that the designed molecules can be highly effective candidates for applications of organic solar cells.

Keywords: DFT; End-capped modification; Non-fully-fused ring acceptors; Organic solar cells.