Tetraphenylmethane-architected porous organic frameworks: Tailorable platforms for sustainable heterogeneous organocatalysis

Organocatalysis plays a pivotal role in sustainable synthesis, yet homogeneous systems suffer from organocatalyst-derived impurities, limited recyclability, and high operational costs. The development of sustainable organocatalysis necessitates critical evaluation of heterogeneous catalyst supports, where porous organic frameworks (POFs) demonstrate unique advantages over conventional platforms. Immobilizing organocatalysts within POFs to create spatially confined reactive sites holds significant promise for addressing key industry challenges—such as the high cost of catalysts, difficult separation from products, elevated operational expenses, and incompatibility with industrial-scale production—thereby paving the way for practical applications. This review highlights tetraphenylmethane-architected POFs ( TPM-POFs ) as ideal platforms for organocatalyst immobilization. The unique tetrahedral geometry of tetraphenylmethane ( TPM ) provides a rigid scaffold that maintains structural integrity while creating well-defined pore architectures. TPM -architected frameworks offer three key advantages: (1) inherent structural rigidity that prevents pore collapse during catalytic processes, (2) versatile functionalization sites through phenyl rings that enable tailored pore environments, and (3) intrinsic lipophilicity that creates favorable microenvironments for organic transformations. A systematic analysis was conducted on the immobilization strategies, catalytic performance, recyclability metrics, and structure-performance correlations for each methodology. Notably, this review elucidates key factors controlling catalytic activity and cycling efficiency of these materials, identifying challenges and opportunities to advance practical, efficient, and cost-effective applications in this field. • Exploring the applications of TPM-POFs in organocatalysis. • Summarizing design strategies for TPM-POFs-supported organocatalysts. • Discussing factors influencing the catalytic performance of TPM-POFs-supported organocatalysts. • Predicting future development directions for TPM-POFs in organic catalysis.