Judicious design alkyl side chain decorated fused aromatic heterocycles as π-spacers has proved to be an efficient strategy to construct highly efficient organic sensitizers. Three novel metal-free dyes W02–04 featuring a highly planar and extensively conjugated 9H-thieno[2′,3':4,5]thieno[3,2-b]thieno[2′,3':4,5]thieno[2,3-d]pyrrole (TTTP) π-bridge have been successfully constructed and applied in dye-sensitized solar cells (DSSCs) for the first time. To better understand the TTTP bridge, the dye W01 possessing the nonplanar 3-hexylthiophene-dithieno[3,2-b:2′,3′-d]pyrrole-3-hexylthiophene linker is prepared as a reference. Introduction of TTTP bridge into the dyes skeleton notably enhances the molar extinction coefficients (ε) by comparison with the reference dye, and much improved short-circuit current (J_sc) have been realized. Meanwhile, dynamics measurements reveal that the charge recombination in devices has been significantly reduced by the incorporation of TTTP bridge. Among these dyes, the DSSCs fabricated with W03 employing cobalt electrolyte achieves an excellent power conversion efficiency of 9.43%, with open-circuit voltage (V_oc) of 848 mV, J_sc of 16.2 mA cm⁻², and fill factor of 0.70 under simulated AM 1.5 G conditions. This work provides important new insight into designing novel organic sensitizers with high ε and efficient suppression of charge recombination.

明智地设计烷基侧链修饰的稠合芳族杂环作为π-间隔基已被证明是构建高效有机敏化剂的有效策略。三种新颖的无金属染料W02 – 04，具有高度平面并广泛共轭的9H-thieno [2'，3'：4,5] thieno [3,2-b] thieno [2'，3'：4,5]噻吩并[2,3-d]吡咯（TTTP）π桥已成功构建并首次应用于染料敏化太阳能电池（DSSC）。为了更好地理解TTTP桥，制备具有非平面3-己基噻吩-二硫代[3,2-b：2'，3'-d]吡咯-3-己基噻吩连接基的染料W01作为参考。在染料骨架中引入TTTP桥显着提高了摩尔消光系数（ε通过与参考染料比较），已经实现了大大改善的短路电流（J _sc）。同时，动力学测量表明，通过引入TTTP电桥，器件中的电荷重组已大大减少。在这些染料中，采用钴电解质的W03制成的DSSC的功率转换效率高达9.43％，开路电压（V _oc）为848 mV，J _sc为16.2 mA cm ^-2，填充系数为0.70。模拟AM 1.5 G条件。这项工作为设计具有高ε值的新型有机敏化剂提供了重要的新见解。 并有效抑制电荷重组。