Relationships Between Defectivity and Porosity in High Surface Area Porous Aromatic Frameworks

Porous aromatic framework (PAF) microporosity is known to be strongly dependent on synthetic approach but little is known about why certain reactions yield significantly and consistently more porous PAFs. This article explores the connections between synthetic pathway, PAF defectivity, and microporosity. Using a network disassembly strategy, we show that defectivity is highly dependent on synthetic approach and that more defective PAFs are associated with lower surface areas and pore volumes. This empirical association is corroborated through systematic introduction of defects to a modelPAF, which results in significant reduction of apparent surface area and pore volumes. Taken together, these data suggest that only highly efficient coupling reactions should be targeted for the synthesis of ultra-high surface area porous aromatic frameworks. Owing to their high apparent surface areas and robust chemical stability, porous aromatic frameworks (PAFs) are being investigated to address a variety of technological challenges where material stability and porosity govern performance. A challenge complicating the synthesis of these materials is the strong dependence of their porosity on synthetic pathway. In this paper, we show that porosity is dependent on defectivity and that defectivity varies significantly between synthetic approaches..**image

Automated summary

This article explores the relationship between synthetic pathway, defectivity, and microporosity of porous aromatic frameworks (PAFs). The results show that defectivity is highly dependent on the synthetic approach and more defective PAFs have lower surface areas and pore volumes. These findings suggest that efficient coupling reactions should be targeted for the synthesis of high surface area PAFs.