Manipulation of Intramolecular Hydrogen Bonds in Conjugated Pseudoladder Polymer for Semiconductivity and Solution-Processability

Abstract

The conformational coplanarity and local rigidity of π-conjugated backbones are critical for the semiconducting performance of organic electronic materials. While fusing the aromatic system into a ladder-type structure effectively enhances these properties, it also often results in poor solution processability and hence limits their transition to device application. To address this challenge, an intramolecularly hydrogen-bonded, full pseudoladder polymer (HPLP) system, based on alternating hydrogen bond donating benzobisimidazole (BBI) and hydrogen bond accepting benzodifuran (BDF) units, is designed and synthesized. A Boc-protected precursor of HPLP allows for feasible solution processing of the polymer into thin films. Subsequently, in situ thermal Boc-deprotection generates the HPLP polymer, in which intramolecular hydrogen bonds form between each pair of neighboring repeating units, inducing coplanarity and rigidity throughout the entire backbone. This is accompanied by a significant red-shift of the absorption spectrum, reduced bandgap, and enhanced rigidity, as confirmed by NMR, UV-Vis, and density functional theory analyses. HPLP films exhibit a three-order-of-magnitude enhancement in charge carrier mobility compared to the Boc-protected precursor and demonstrate excellent solvent resistance in organic thin-film transistors.

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Article information

Article type
Paper
Submitted
31 Mar 2025
Accepted
04 Jul 2025
First published
07 Jul 2025
This article is Open Access
Creative Commons BY-NC license

J. Mater. Chem. C, 2025, Accepted Manuscript

Manipulation of Intramolecular Hydrogen Bonds in Conjugated Pseudoladder Polymer for Semiconductivity and Solution-Processability

O. Miranda, P. Mantegazza, V. N. Shinde, Z. Cao, S. Shelton, S. Moro, C. Deverter, Y. Liu, X. Gu, G. Costantini and L. Fang, J. Mater. Chem. C, 2025, Accepted Manuscript , DOI: 10.1039/D5TC01365H

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