The ability to deliver electrons is vital for dye-based photocatalysts. Conventionally, the aromatic stacking-based charge-transfer complex increases photogenerated electron accessibility but decreases the energy of excited-state dyes. To circumvent this dilemma, here we show a strategy by tuning the stacking mode of dyes. By decorating naphthalene diimide with S-bearing branches, the S···S contact-linked naphthalene diimide string is created in coordination polymer, thereby enhancing electron mobility while simultaneously preserving competent excited-state reducing power. This benefit, along with in situ assembly between naphthalene diimide strings and exogenous reagent/reactant, improves the accessibility of short-lived excited states during consecutive photon excitation, resulting in greater efficiency in photoinduced electron-transfer activation of inert bonds in comparison to other coordination polymers with different dye-stacking modes. This heterogeneous approach is successfully applied in the photoreduction of inert aryl halides and the successive formation of C_Ar−C/S/P/B bonds with potential pharmaceutical applications.

传递电子的能力对于染料基光催化剂至关重要。传统上，基于芳香族堆叠的电荷转移络合物增加了光生电子的可及性，但降低了激发态染料的能量。为了避免这种困境，我们在这里展示了一种通过调整染料堆叠模式的策略。通过用含S支链修饰萘二酰亚胺，在配位聚合物中形成S·S接触连接的萘二酰亚胺链，从而增强电子迁移率，同时保持足够的激发态还原能力。这种好处以及萘二酰亚胺串和外源试剂/反应物之间的原位组装，提高了连续光子激发期间短寿命激发态的可及性，与具有不同染料堆积模式的其他配位聚合物相比，惰性键的光诱导电子转移激活效率更高。这种非均相方法成功应用于惰性芳基卤化物的光还原和C的连续形成_Ar -C/S/P/B 与潜在的药物应用结合。