Thieno[3,2-b]thiophene−diketopyrrolopyrrole derivatives: Revised and scalable synthesis, optical and electronic properties
Abstract
Thieno[3,2- b ]thiophene-based diketopyrrolopyrrole (DPP) derivatives are highly promising building blocks for low-bandgap organic semiconductors, yet their dialdehyde counterparts remain underexplored due to limited synthetic accessibility. Herein, we report an optimized and scalable synthesis of the thieno[3,2- b ]thiophene DPP dialdehyde, featuring an efficient one-pot introduction of a nitrile functionality and enabling multigram-scale production. This key intermediate was subsequently employed to prepare a series of π-conjugated small molecules of A–D–A–D–A structure via a straightforward Knoevenagel condensation with various acceptor units, thus avoiding the use of organometallic cross-coupling reactions. The resulting materials exhibit broad optical absorption and low bandgaps, with electrochemical and optical bandgaps in the ranges of 1.05–1.50 eV and 1.43–1.62 eV, respectively. The tetranitrofluorene DPP derivative synthesized displays the lowest electronic bandgap (1.05 eV), highlighting the effectiveness of conjugation extension of this π-conjugated system. Experimental results are in good agreement with time-dependent density functional theory calculations, with the HSE06 functional providing the most accurate description of frontier orbital energies. When evaluated in organic field-effect transistors, the materials show n -type behavior, with the tetracyano DPP derivative exhibiting the highest electron mobility, reaching (2.8 ± 0.4) × 10⁻³ cm²·V⁻¹·s⁻¹ after thermal annealing. Overall, this work demonstrates that thieno[3,2- b ]thiophene DPP dialdehyde is a versatile and synthetically accessible platform for the development of low-bandgap organic semiconductors via a metal-free strategy, opening new possibilities for scalable and high-performance electronic materials.
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BibTeX
@article{joly2026thieno32bthiophenediketopyrrolopyrrole,
title = {{Thieno[3,2-b]thiophene−diketopyrrolopyrrole derivatives: Revised and scalable synthesis, optical and electronic properties}},
author = {Léa Joly and Thibaut Jarrosson and Jean-Noël Volle and Aimilia Papasouli and Ali Chahine and Panagiotis Karamanis and Patrick Lévêque and Françoise Serein-Spirau and Claude Niebel},
journal = {Synthetic Metals},
year = {2026},
month = oct,
doi = {10.1016/j.synthmet.2026.118267},
url = {https://hal.umontpellier.fr/hal-05781025v1},
note = {CC BY},
}
RIS
TY - JOUR
TI - Thieno[3,2-b]thiophene−diketopyrrolopyrrole derivatives: Revised and scalable synthesis, optical and electronic properties
AU - Léa Joly
AU - Thibaut Jarrosson
AU - Jean-Noël Volle
AU - Aimilia Papasouli
AU - Ali Chahine
AU - Panagiotis Karamanis
AU - Patrick Lévêque
AU - Françoise Serein-Spirau
AU - Claude Niebel
PY - 2026
DA - 2026/10/06
JO - Synthetic Metals
DO - 10.1016/j.synthmet.2026.118267
UR - https://hal.umontpellier.fr/hal-05781025v1
AB - Thieno[3,2- b ]thiophene-based diketopyrrolopyrrole (DPP) derivatives are highly promising building blocks for low-bandgap organic semiconductors, yet their dialdehyde counterparts remain underexplored due to limited synthetic accessibility. Herein, we report an optimized and scalable synthesis of the thieno[3,2- b ]thiophene DPP dialdehyde, featuring an efficient one-pot introduction of a nitrile functionality and enabling multigram-scale production. This key intermediate was subsequently employed to prepare a series of π-conjugated small molecules of A–D–A–D–A structure via a straightforward Knoevenagel condensation with various acceptor units, thus avoiding the use of organometallic cross-coupling reactions. The resulting materials exhibit broad optical absorption and low bandgaps, with electrochemical and optical bandgaps in the ranges of 1.05–1.50 eV and 1.43–1.62 eV, respectively. The tetranitrofluorene DPP derivative synthesized displays the lowest electronic bandgap (1.05 eV), highlighting the effectiveness of conjugation extension of this π-conjugated system. Experimental results are in good agreement with time-dependent density functional theory calculations, with the HSE06 functional providing the most accurate description of frontier orbital energies. When evaluated in organic field-effect transistors, the materials show n -type behavior, with the tetracyano DPP derivative exhibiting the highest electron mobility, reaching (2.8 ± 0.4) × 10⁻³ cm²·V⁻¹·s⁻¹ after thermal annealing. Overall, this work demonstrates that thieno[3,2- b ]thiophene DPP dialdehyde is a versatile and synthetically accessible platform for the development of low-bandgap organic semiconductors via a metal-free strategy, opening new possibilities for scalable and high-performance electronic materials.
SN - 0379-6779
ER -