Side chain effect on the electrochemical and optical properties of thieno[3,4-c]pyrrole-4,6-dione based donor–acceptor donor type monomers and polymers

Abstract

In organic π-conjugated materials, side chains play great roles that impact far beyond solubility. In this work, we mainly focused on the synthesis of new donor–acceptor–donor (D–A–D) type conjugated monomers and their corresponding polymers appending thieno[3,4-c]pyrrole-4,6-dione (TPD) acceptor with a new side chain, fluorene (Fl), to investigate the side chain effect. In this context, to reveal the precise effect of the side chains on the optical and electrochemical properties of the monomers and polymers synthesized in this work, four series of D–A–D monomers, each containing a TPD core unit with a different side chain, are compared and discussed in relation to each other. Notably, it was discovered that the TPD acceptor unit can be modified with any functional group other than common alkyl chains to impart new functionalities by maintaining their superior optoelectronic properties. New types of side chains can be used to tune the physical characteristics, such as solubility, absorption, emission, and molecular packing. In this work, Fl-appended monomers as a new class of D–A–D type π-conjugated molecules containing 3,4-ethylenedioxythiophene (EDOT (E)) and 3,4-propylenedioxythiophene (ProDOT (P)) donor units were studied and it was found that 1,3-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-5-(9H-fluoren-2-yl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione (E(Fl)) and 1,3-bis(3,3-didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)-5-(9H-fluoren-2-yl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione (P(Fl)) exhibited reasonable quantum yields and their corresponding polymers revealed ambipolar character with slightly lower band gap as compared to the previous analogues containing other side chains. Observed experimental results were elucidated by first principle calculations. In this paper, we discussed that using side chain engineering is an effective strategy for improving next-generation organic π-conjugated materials with the desired properties.