The mild and sustainable methods for CH direct trifluoromethylation of (hetero)arenes without any base or strong oxidants are in extremely high demand. Here, we report that the photo-generated electron-hole pairs of classical semiconductors (CdS or g-C₃N₄) under visible light excitation are effective to drive CH trifluoromethylation of (hetero)arenes with stable and inexpensive CF₃SO₂Na as the trifluoromethyl (TFM) source via radical pathway. Either CdS or g-C₃N₄ propagated reaction can efficiently transform CF₃SO₂Na to CF₃ radical and further afford the desired benzotrifluoride derivatives in moderate to good yields. After visible light initiated photocatalytic process, the key elements (such as F, S and C) derived from the starting TFM source of CF₃SO₂Na exhibited differential chemical forms as compared to those in other oxidative reactions. The photogenerated electron was trapped by chemisorbed O₂ on photocatalysts to form superoxide radical anion (O₂⁻) which will further attack CF₃ radical with the generation of inorganic product F⁻ and CO₂. This resulted in a low utilization efficiency of CF₃ (<50%). When nitro aromatic compounds and CF₃SO₂Na served as the starting materials in inert atmosphere, the photoexcited electrons can be directed to reduce the nitro group to amino group rather than being trapped by O₂. Meanwhile, the photogenerated holes oxidize SO₂CF₃⁻ into CF₃. Both the photogenerated electrons and holes were engaged in reductive and oxidative paths, respectively. The desired product, trifluoromethylated aniline, was obtained successfully via one-pot free-radical synthesis.

非常需要温和且可持续的方法，用于（杂）芳烃的C H直接三氟甲基化，无需任何碱或强氧化剂。在这里，我们报道了在可见光激发下经典半导体（CdS或gC ₃ N ₄）的光生电子-空穴对有效地驱动了具有稳定且廉价的CF ₃ SO ₂ Na作为（杂）芳烃的C H三氟甲基化。三氟甲基（TFM）来源通过自由基途径。CdS或gC ₃ N ₄传播的反应均可有效地将CF ₃ SO ₂ Na转化为CF ₃自由基并进一步以中等至良好的产率提供所需的苯并三氟衍生物。在可见光引发的光催化过程之后，与其他氧化反应相比，衍生自CF ₃ SO ₂ Na的起始TFM源的关键元素（例如F，S和C）表现出不同的化学形式。光生电子被截留通过化学吸附Ò ₂上的光催化剂以形成超氧阴离子自由基（O ₂ ^- ），这将进一步攻击CF ₃基团与无机乘积F的生成^-和CO ₂。这导致CF _3的利用率较低（<50％）。当在惰性气氛中以硝基芳族化合物和CF ₃ SO ₂ Na作为起始原料时，可以将光激发电子导向以将硝基还原为氨基，而不是被O ₂捕获。同时，光生空穴氧化SO ₂ CF ₃ ^-成CF ₃。光生电子和空穴分别参与还原和氧化途径。通过一锅自由基合成法成功获得所需产物三氟甲基化苯胺。