Thienoisoindigo-based recyclable conjugated polymers for organic electronics

Abstract

Imine-based semiconducting polymers based on thiophene-flanked diketopyrrolopyrrole (TDPP) are widely used to realize naturally disposable electronic devices. However, TDPP easily decomposes under mildly acidic conditions, limiting its potential for use in recyclable systems. Herein, we designed and synthesized two chemically recyclable thienoisoindigo (TII)-based polymers bearing an imine bond. These polymers were prepared from polycondensation reactions of the dialdehyde-functionalized monomer TII-(CHO)₂ with p-phenylenediamine (PD) to produce p(TII-PD) and with 2,6-naphthalenediamine (2,6ND) to produce p(TII-2,6ND), respectively. Using ultraviolet-visible-near infrared spectroscopy, nuclear magnetic resonance, and mass spectroscopy, we examined the recyclability of both polymers. Under mildly acidic conditions, the imine-based polymers fully degrade into the original TII-(CHO)₂ in as little as one day. Moreover, the recovered TII-(CHO)₂ monomer is chemically stable for up to 6 months under acidic conditions, allowing us to isolate the monomer in high yield (>90%). Using the recovered TII-(CHO)₂ monomer, we prepared recycled polymers, re-p(TII-PD) and re-p(TII-2,6ND). The recycled polymers displayed nearly the same electrical properties as the pristine polymers, with field-effect transistor mobilities in the order of 10⁻²–10⁻³ cm² V⁻¹ s⁻¹. These results demonstrate the versatility of the TII-based monomer unit for developing fully recyclable semiconducting polymers.