Semiconducting organic polymers with donor-acceptor units are of great interest due to their superior properties. Tuning the HOMO and LUMO levels with different donors and acceptors makes it possible to design polymers with desired electronic, optical, and molecular properties. In this paper, commercially available donors (thieno[3,4-b]pyrazine (TP), thieno[3,4-b]quinoxaline (TQ), 2H-pyrrolo[3,4-b]quinoxaline (PQ), 6H-pyrrolo[3,4-b]pyrazine (PP)) and acceptors (benzo[c][1,2,5]thiadiazole (BT), naphtho[2,3-c][1,2,5]thiadiazole (NT)) were selected to form monomers (TP-BT, TP-NT, TQ-BT, TQ-NT, PP-BT, PP-NT, PQ-BT, PQ-NT) that were used to design D-A type copolymers. The electronic and optical properties of the monomers and oligomers were theoretically investigated using DFT/B3LYP/6-31G** and TD-DFT/B3LYP/6-31G** methods. The HOMO and LUMO levels of the designed polymers ranged from −5.05 to −4.18 eV and from −3.05 to −3.57 eV, respectively. Estimated electronic band gaps of these polymers were obtained as 0.79–2.00 eV within the range of semiconductor values. It is indicated that TQ/PQ units as donors and BT as an acceptor is the suggestible combination to design low band gap polymer which is easily synthesizable through direct arylation polymerization of brominated acceptors with donors. The presented approach provides a valuable guide for experimental studies to design new types of semiconducting organic polymers.

具有供体-受体单元的半导体有机聚合物由于其优异的性能而备受关注。使用不同的供体和受体调节 HOMO 和 LUMO 能级，可以设计具有所需电子、光学和分子特性的聚合物。在本文中，可商购的供体（噻吩并[3,4- b ]吡嗪（TP），噻吩并[3,4- b ]喹喔啉（TQ），2 ^ h -吡咯并[3,4- b ]喹喔啉（PQ）， 6 H-吡咯并[3,4- b ]吡嗪( PP ))和受体(苯并[ c ][1,2,5]噻二唑( BT )、萘并[2,3- c]] [1,2,5]噻二唑（NT））被选定形式的单体（TP - BT，TP - NT，TQ - BT，TQ - NT，P P - BT，P P - NT，PQ - BT，PQ -新台币) 用于设计 DA 型共聚物。使用 DFT/B3LYP/6-31G** 和 TD-DFT/B3LYP/6-31G** 方法从理论上研究了单体和低聚物的电子和光学性质。设计的聚合物的 HOMO 和 LUMO 能级分别为 -5.05 至 -4.18 eV 和 -3.05 至 -3.57 eV。这些聚合物的估计电子带隙在半导体值范围内为 0.79-2.00 eV。表明TQ / PQ单位作为捐助者和BT作为受体是设计低带隙聚合物的建议组合，该聚合物易于通过溴化受体与供体的直接芳基化聚合而合成。所提出的方法为设计新型半导体有机聚合物的实验研究提供了宝贵的指导。