A molecular-Lego approach to fluorinated phosphine-containing polymers enables efficient CO₂ transformation

Abstract

Phosphine-containing porous organic polymers are candidate materials that could realize heterogenization of the homogeneous phosphine-metal catalysts. However, their succinct synthesis from the commercialized phosphines directly is still a challenge. This work pioneers a Brønsted acid-catalyzed molecular Lego assembly, enabling modular construction of fluorinated phosphine-containing polymers (FPPs) from commercial building blocks - aryl phosphines or their metal complexes - in one step. By simply introducing a third molecular-Lego module with rigid skeleton (e.g., spirobifluorene, triptycene), the porosity of FPPs can be precisely engineered while maintaining good to high yields (60%-98%), demonstrating the plug-and-play versatility of this strategy. This work presents the synthesis of 18 different structures of FPPs with distinct structures. Among them, the Ru complex-derived FPPs-10 shows excellent CO₂ uptake capability (1.15 mmol·g^-1 at 0 °C) and exhibits exceptional performance in N-formylation reaction: high activity (turnover number up to 1.41 × 10⁵), and good stability (reused at least for 5 cycles), while maintaining broad alkylamine compatibility. Overall, this work establishes a molecular Lego-like assembly paradigm for the on-demand design and regulation of phosphine-based heterogeneous catalysts.

Keywords

Porous phosphine-containing polymers / molecular Lego / heterogeneous catalysis / carbon dioxide / N-formylation

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