Photoredox and organo-catalysis denote powerful construction tools for new classes of carbon–carbon bonds, where incisive amalgamation of both the approaches over a single, recyclable platform can bring about synergic and eco-friendly reactions under mild conditions. Aiming at enamine-based photoredox catalysis for atom-economic and metal-free sp³ CH activation, an amide-based two-dimensional (2D) porous organic framework (POF) is devised. The pendent NH₂ groups are judiciously anchored with two catalytic stations viz. Rose Bengal and L-proline, through stepwise variation of solid phase peptide synthesis. The dual-catalyst engineered POF represents a fully organic material that synergistically performs visible-light triggered oxidative Mannich reaction to produce biorelevant heterocycle β-amino ketone in excellent yield at room temperature, using oxygen as clean and selective oxidant. Importantly, activity of this bi-functionalized catalyst compares favorably well to individual homogeneous counterparts. The covalently modified framework demonstrates economic viability via gram-scale synthesis besides admirable reusability, and proves to be effective for nineteen varieties of substrates. The photocatalytic path is detailed from efficient energy transfer from host polymer to substrate in light of experimental and theoretical studies, which provides proof-of-concept to the photo-organo combined mechanism. The material benefits heterogenising two homogeneous catalysts, besides excluding additional steps of conventional Mannich reactions, and offers a step-forward to smart and green cross-dehydrogenative coupling reactions.

光氧化还原和有机催化代表了新型碳-碳键的强大构建工具，在温和的条件下，两种方法在单个可回收平台上的精细融合可在环境下产生协同和生态友好的反应。旨在基于烯胺的光氧化还原催化原子经济和无金属的sp ³ C H活化，设计了一种基于酰胺的二维（2D）多孔有机骨架（POF）。下垂的NH ₂各组明智地锚定有两个催化站。玫瑰孟加拉和L-脯氨酸，通过逐步改变固相肽合成。双催化剂工程化的POF代表一种完全有机的材料，它可以在室温下协同地执行可见光触发的氧化曼尼希反应，以氧气的清洁和选择性氧化剂的优异收率生产生物相关的杂环β-氨基酮。重要的是，这种双官能化催化剂的活性与单独的均相对应物相比非常好。共价修饰的框架除具有令人称赞的可重复使用性外，还通过克级合成证明了经济可行性，并被证明对19种底物有效。根据实验和理论研究，详细说明了从主体聚合物到底物的有效能量转移的光催化路径，这为光有机结合机理提供了概念验证。除了排除常规曼尼希反应的额外步骤外，该材料还有利于使两种均相催化剂均质化，并为智能和绿色的交叉脱氢偶联反应提供了一个进步。