Litcius/Paper detail

Chalcogen-bridged coordination polymer for the photocatalytic activation of aryl halides

Le Zeng, Tiexin Zhang, Renhai Liu, Wenming Tian, Kaifeng Wu, Jingyi Zhu, Zhonghe Wang, Cheng He, Jing Feng, Xiangyang Guo, Abdoulkader Ibro Douka, Chunying Duan

2023Nature Communications38 citationsDOIOpen Access PDF

Abstract

Abstract 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.

Topics & Concepts

StackingPhotochemistryExcited stateArylElectron transferMaterials scienceDiimideChalcogenChemistryPhotocatalysisCrystallographyMoleculePeryleneOrganic chemistryNuclear physicsAlkylPhysicsCatalysisMetal-Organic Frameworks: Synthesis and ApplicationsRadical Photochemical ReactionsPerovskite Materials and Applications