Theoretical Investigation of Optical and Electronic Property Modulations of π-Conjugated Polymers Based on the Electron-Rich 3,6-Dimethoxy-fluorene Unit.

Poly(fiuorene)-type materials are widely used in polymer-based emitting devices. One of the drawbacks of light-emitting diodes based on polyfiuorene derivatives is the injection of holes from the anode due to the high ionization potential (IP) of most derivatives. Substitution by electrondonating alkoxy substituents or by adding charge carriers on the conjugated polymer's backbone produces a remarkable influence on its electrical and optical properties. In this contribution, we apply quantum-chemical techniques to investigate a family of π-conjugated polymers with substituted dimethoxy groups at the 3,6 positions of the fiuorene ring, namely, poly(2,7-(3,6dimethoxy-fiuorene)(PDMOF), poly(2,7-(3,6-dimethoxy-fiuorene)-co-alt-fiuorene (PDMOFF), and poly(2,7-(3,6-dimeth-oxy-fiuorene)-co-alt-2,5-thiophene (PDMOFT). The electronic properties of the neutral molecules, HOMO-LUMO gaps (ΔH-L), in addition to the positive and negative ions, are studied using the B3LYP functional. The lowest excitation energies (Eg) and the maximal absorption wavelength Λabs of PDMOF, PDMOFF, and PDMOFT are studied by employing time-dependent density functional theory (TD-DFT) and the ZINDO semiempirical method. The IP, EA, and Eg values of each polymer were obtained by extrapolating those of the oligomers to the inverse chain length equal to zero (1/n = 0). The influence of the presence of methoxy groups on the fiuorene moiety on the ionization potential is especially emphasized. The outcomes show that the HOMO energies of these systems under study increase by about 0.4 eV and the IP values decrease by about 0.3 eV compared to those of the corresponding polyfiuorene. Both effects result in a reduction of the energy barrier for the injection of holes in related polymeric light-emitting devices and should contribute to the enhancement of their performances. Because of the cooperation with thiophene in PDMOFT, which results in a good planar conformation, both the hole-creating and electronaccepting abilities are improved. [ABSTRACT FROM AUTHOR]