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

Abstract

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.

Construction of Porous Aromatic Frameworks with Specifically Designed Motifs for Charge Storage and Transport

“…Meanwhile, the reacting efficiency is also important to minimize the formation of defects. The Ni(0) catalyzed Yamamoto type Ullmann coupling reaction is considered as most effective to build highly porous PAFs . For a long time, the coupling reactions have been only focused on those formed C–C single bonds, but recently, other reactions that built conjugated connections, diacetylene and aromatic cyclic have found their usages to incorporate motifs in the frameworks for specific functions (Figure b). , …”