Dynamic covalent chemistry, with its ability to correct synthetic dead-ends, allows for the synthesis of elaborate extended network materials in high yields. However, the limited number of reactions amenable to dynamic covalent chemistry necessarily confines the scope and functionality of materials synthesized. Here, we explore the dynamic and self-correcting nature of nucleophilic aromatic substitution (S_NAr), using ortho-aryldithiols and ortho-aryldifluorides that condense to produce redox-active thianthrene units. We demonstrate the facile construction of two-, three- and four-point junctions by reaction between a dithiol nucleophile and three different model electrophiles that produces molecules with two, three and four thianthrene moieties, respectively, in excellent yields. The regioselectivity observed is driven by thermodynamics; other connections form under kinetic control. We also show that the same chemistry can be extended to the synthesis of novel ladder macrocycles and porous polymer networks with Brunauer–Emmett–Teller surface area of up to 813 m² g⁻¹.

动态共价化学具有纠正合成死角的能力，可以高产率合成精细的延伸网络材料。然而，适合于动态共价化学反应的有限数量的反应必然限制了合成材料的范围和功能。在这里，我们使用邻-芳基二硫醇和邻-芳基二硫醇探索亲核芳族取代（S _N Ar）的动态和自我校正性质缩合生成氧化还原活性的蒽单元的-芳基二氟化物。我们通过二硫醇亲核体和三种不同模型的亲电体之间的反应证明了两点，三点和四点连接的简便构建，该亲电体分别产生具有两个，三个和四个噻蒽部分的分子，并具有极高的收率。观察到的区域选择性是由热力学驱动的。其他连接在动力学控制下形成。我们还表明，相同的化学性质可以扩展到Brunauer-Emmett-Teller表面积高达813 m ²  g ^-1的新型梯形大环化合物和多孔聚合物网络的合成。