Jismy Badr, Durand Pablo, Jacob Jasmine P, Richard Fanny, Boyron Olivier, Heinrich Benoit, Schmaltz Bruno, Lévêque Patrick, Bardagot Olivier, Leclerc Nicolas
Institute of Chemistry and Processes for Energy Environment and Health (ICPEES), CNRS, University of Strasbourg, 25 rue de Becquerel, Strasbourg, 67087, France.
Laboratoire de Physico-Chimie des Matériaux et des Electrolytes pour l'Energie (PCM2E), Université de Tours, EA6299, Tours, 37200, France.
Macromol Rapid Commun. 2025 Aug;46(16):e2500243. doi: 10.1002/marc.202500243. Epub 2025 May 13.
A series of novel conjugated semiconducting polymers based on the unsubstituted thiazolo[5,4-d]thiazole (TzTz) unit is synthesized using atom-economic and environmentally friendly direct (hetero)arylation polymerization (DHAP). The versatility of the proposed polymerization conditions, employing a non-chlorinated and moderately toxic solvent and cooperative palladium/copper bimetallic catalytic system, is demonstrated through the use of seven comonomers with varying electron-withdrawing strength: 2,2'-bithiophene (BT), 6,7-difluoroquinoxaline (Qx), thieno[3,4-c]pyrrole-4,6(5H)-dione (TPD), 5,6-difluorobenzo[c][1,2,5]thiadiazole (BTD), isoindigo (IID), para-azaquinodimethane (AQM) and 2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (DPP). The resulting TzTz-based copolymers exhibit optical bandgaps between 1.5 and 2.0 eV with HOMO/LUMO energy levels spanning from -5.2/-3.3 eV to -5.4/-3.9 eV. They all show satisfactory thermal stability for electronic applications (Td = 300-360 °C). Notably, TzTz-based copolymers are observed they generally exhibit improved backbone planarity and deeper LUMO levels than their thiophene derivatives. A synthesis tool to finely lower the LUMO levels of next-generation A-A' copolymers in view of increasing the performance and air-stability of doped organic electronics is believed to be provided by this work.
采用原子经济性和环境友好的直接（杂）芳基化聚合（DHAP）方法，合成了一系列基于未取代噻唑并[5,4-d]噻唑（TzTz）单元的新型共轭半导体聚合物。通过使用七种具有不同吸电子强度的共聚单体：2,2'-联噻吩（BT）、6,7-二氟喹喔啉（Qx）、噻吩并[3,4-c]吡咯-4,6(5H)-二酮（TPD）、5,6-二氟苯并[c][1,2,5]噻二唑（BTD）、异靛蓝（IID）、对氮杂喹二亚甲基（AQM）和2,5-二氢吡咯并[3,4-c]吡咯-1,4-二酮（DPP），证明了所提出的聚合条件的通用性，该条件采用非氯化且毒性适中的溶剂以及钯/铜双金属协同催化体系。所得的基于TzTz的共聚物的光学带隙在1.5至2.0 eV之间，其最高占据分子轨道（HOMO）/最低未占据分子轨道（LUMO）能级范围为-5.2/-3.3 eV至-5.4/-3.9 eV。它们都表现出对电子应用而言令人满意的热稳定性（热分解温度Td = 300 - 360 °C）。值得注意的是，观察到基于TzTz的共聚物通常比其噻吩衍生物表现出更好的主链平面性和更深的LUMO能级。这项工作有望提供一种合成工具，用于精细地降低下一代A - A'共聚物的LUMO能级，以提高掺杂有机电子器件的性能和空气稳定性。
