Intermolecular Charge Transfer in Perylenediimide-Based Crystalline Materials for Near-Infrared Photothermal Conversion and Photocatalytic Organic Transformations

The rational design and development of novel intermolecular charge-transfer materials for applications such as near-infrared (NIR) photothermal conversion and as photocatalysts of organic transformations is currently a challenge. Perylenediimides (PDIs) are a remarkable class of organic dyes featuring electron-deficient planes, with fast-response photoinduced electron transfer and charge separation properties. In this work, we report a PDI-based coordination polymer (Zn-PMPDI-Cl 4 ) as a host framework engineered as a charge-transfer material with exceptional stability and tunability. Zn-PMPDI-Cl 4 can generate radical anions (Zn-PMPDI-Cl 4 •– ) in situ through photoinduced electron transfer, with dimethylamine as the electron donor. Due to the strong NIR absorption and high stability of the radical anions, the material exhibits highly efficient photothermal conversion performance and good recyclability. Zn-PMPDI-Cl 4 demonstrated high photocatalytic activity in sulfide oxidation and amine oxidative coupling reactions, delivering high yields with broad substrate scope and excellent recyclability. This catalytic performance originates from photoinduced electron transfer between the substrate and the electron-deficient PDI core.