Markushyna Yevheniia, Schüßlbauer Christoph M, Ullrich Tobias, Guldi Dirk M, Antonietti Markus, Savateev Aleksandr
Department of Colloid Chemistry, Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1, 14476, Potsdam, Germany.
Department of Chemistry and Pharmacy, Interdisciplinary Center for Molecular Materials(ICMM), Friedrich-Alexander University of Erlangen-Nürnberg, Egerlandstrasse 3, 91058, Erlangen, Germany.
Angew Chem Int Ed Engl. 2021 Sep 6;60(37):20543-20550. doi: 10.1002/anie.202106183. Epub 2021 Aug 8.
Among external stimuli used to promote a chemical reaction, photocatalysis possesses a unique one-light. Photons are traceless reagents that provide an exclusive opportunity to alter chemoselectivity of the photocatalytic reaction varying the color of incident light. This strategy may be implemented by using a sensitizer capable to activate a specific reaction pathway depending on the excitation light. Herein, we use potassium poly(heptazine imide) (K-PHI), a type of carbon nitride, to generate selectively three different products from S-arylthioacetates simply varying the excitation light and otherwise identical conditions. Namely, arylchlorides are produced under UV/purple, sulfonyl chlorides with blue/white, and diaryldisulfides at green to red light. A combination of the negatively charged polyanion, highly positive potential of the valence band, presence of intraband states, ability to sensitize singlet oxygen, and multi-electron transfer is shown to enable this chromoselective conversion of thioacetates.
在用于促进化学反应的外部刺激中，光催化具有独特的“一光多用”特性。光子是无痕试剂，它提供了一个独特的机会，通过改变入射光的颜色来改变光催化反应的化学选择性。该策略可通过使用一种敏化剂来实现，该敏化剂能够根据激发光激活特定的反应途径。在此，我们使用聚（七嗪酰亚胺）钾（K-PHI），一种氮化碳，在其他条件相同的情况下，仅通过改变激发光就可以从S-芳基硫代乙酸酯中选择性地生成三种不同的产物。具体而言，在紫外/紫光照射下生成芳基氯，在蓝/白光照射下生成磺酰氯，在绿光至红光照射下生成二芳基二硫化物。研究表明，带负电荷的聚阴离子、价带的高正电位、带内态的存在、单线态氧敏化能力以及多电子转移的结合使得硫代乙酸酯能够实现这种颜色选择性转化。
