An anionic two dimensional covalent organic framework from tetratopic borate centres pillared by lithium ions

Abstract Non-covalent interactions play an important role for the framework formation of two-dimensional covalent organic frameworks. Until now, π–π interactions and hydrogen bonding are the main reported forces facilitating the stacking of framework layers. Here, we present a two-dimensional anionic covalent organic framework based on tetratopic borate linkages, where layers are connected by ionic interactions between the linkage site and counter cations. The crystalline covalent organic framework is accessed through the formation of an amorphous borate-based polymer and subsequent solvothermal treatment. The progress of crystallization is investigated, revealing the crystallite growth and morphological change from agglomerated dense particles to hollow crystallite spheres. Due to the pillared nature, the crystallites can be exfoliated into nanosheets by sonication of the material in the presence of methanol. The crystallization and ordered arrangement of the lithium ions in the interlayer space is shown to benefit the conductivity tenfold compared to the amorphous material.