Enhancing structural control in covalent organic frameworks through steric interaction-driven linker design

Covalent Organic Frameworks (COFs) exhibiting kagome (kgm) structures are promising crystalline porous materials with two distinct pores. However, there are no reliable synthetic methods to exclusively target the kgm over the polymorphic square-lattice (sql) structure. To address this, we introduce a linker design strategy featuring bulky functional groups, which through steric interactions can hinder the sql net formation, thereby leading to a kgm structure. By rigid attachment of the methyl benzoate groups to a tetradentate COF linker, steric interactions with neighbouring linkers depending on the pore size become possible. The steric interaction was tuned by varying the complementary bidentate linear linker lengths, where the shorter phenylenediamine linker leads to steric hindrance and the formation of the kgm lattice, while with the longer benzidine linker, steric interaction is reduced leading to the sql lattice. Thus, control over the net can be exerted through steric interaction strengths. Additionally, structural analysis revealed the formation of the kgm COF with an unusual ABC stacking, leading to pearl string type pores instead of two distinct pore sizes. This COF system shows that steric interaction-driven design enhances control over COF structures, expanding the design toolbox, but also provides valuable insights into network formation and polymorphism.