Photoexcitation of the electron-donor-acceptor complexes have been an effective approach to achieve radicals by triggering electron transfer. However, the catalytic version of electron-donor-acceptor complex photoactivation is quite underdeveloped comparing to the well-established utilization of electronically biased partners. In this work, we utilize 4-nitrophthalonitrile as an electron acceptor to facilitate the efficient π-stacking with electron-rich aromatics to form electron-donor-acceptor complex. The characterization and energy profiles on the cocrystal of 4-nitrophthalonitrile and 1,3,5-trimethoxybenzene disclose that the electron transfer is highly favorable under the light irradiation. This electron acceptor catalyst can be efficiently applied in the benzylic C−H bond photoactivation by developing the Giese reaction of alkylanisoles and the oxidation of the benzyl alcohols. A broad scope of electron-rich aromatics can be tolerated and a mechanism is also proposed. Moreover, the corresponding π-anion interaction of 4-nitrophthalonitrile with potassium formate can further facilitate the hydrocarboxylation of alkenes efficiently.

电子供体-受体复合物的光激发是通过触发电子转移来产生自由基的有效方法。然而，与电子偏压伙伴的成熟利用相比，电子供体-受体复合物光活化的催化版本还相当不发达。在这项工作中，我们利用4-硝基邻苯二甲腈作为电子受体，促进与富电子芳香族化合物的有效π堆积，形成电子供体-受体复合物。 4-硝基邻苯二甲腈和1,3,5-三甲氧基苯共晶的表征和能量分布表明，在光照射下电子转移非常有利。通过发展烷基苯甲醚的吉斯反应和苯甲醇的氧化，这种电子受体催化剂可以有效地应用于苯甲基CH键光活化。可以容忍范围广泛的富电子芳香族化合物，并且还提出了一种机制。此外，4-硝基邻苯二甲腈与甲酸钾相应的π阴离子相互作用可以进一步促进烯烃的有效加氢羧化。