A Heteromeric Carboxylic Acid Based Single‐Crystalline Crosslinked Organic Framework. Issue 43 (20th September 2021) - Liang, Rongran
Abstract: The development of large pore single‐crystalline covalently linked organic frameworks is critical in revealing the detailed structure‐property relationship with substrates. One emergent approach is to photo‐crosslink hydrogen‐bonded molecular crystals. Introducing complementary hydrogen‐bonded carboxylic acid building blocks is promising to construct large pore networks, but these molecules often form interpenetrated networks or non‐porous solids. Herein, we introduced heteromeric carboxylic acid dimers to construct a non‐interpenetrated molecular crystal. Crosslinking this crystal precursor with dithiols afforded a large pore single‐crystalline hydrogen‐bonded crosslinked organic framework HC OF‐101. X‐ray diffraction analysis revealed HC OF‐101 as an interlayer connected hexagonal network, which possesses flexible linkages and large porous channels to host a hydrazone photoswitch. Multicycle Z/E‐isomerization of the hydrazone took place reversibly within HC OF‐101, showcasing the potential use of HC OF‐101 for optical information storage. Abstract : A large pore single‐crystalline hydrogen‐bonded crosslinked organic framework was synthesized through heteromeric monomer co‐crystallization followed by thiol–ene crosslinking. The crosslinked porous crystals featured large pores to host a hydrazone switch for solid‐state photo‐patterning.