A Heteromeric Carboxylic Acid Based Single‐Crystalline Crosslinked Organic Framework

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 carbo...

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Bibliographic Details
Published in:Angewandte Chemie (International ed.) 2021-10, Vol.60 (43), p.23176-23181
Main Authors: Liang, Rongran, Samanta, Jayanta, Shao, Baihao, Zhang, Mingshi, Staples, Richard J., Chen, Albert D., Tang, Miao, Wu, Yuyang, Aprahamian, Ivan, Ke, Chenfeng
Format: Article
Language:English
Subjects:
Carboxylic acids
Chemical bonds
Crosslinking
Crystal structure
Crystallinity
Crystals
Dimers
heteromeric carboxylic acid dimer
Hydrazones
Hydrogen
hydrogen-bonded crosslinked organic framework
Information storage
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Interlayers
Interpenetrating networks
Isomerization
photo-switch
single-crystal to single-crystal transformation
single-crystalline porous organic material
Substrates
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Summary: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 HCOF‐101. X‐ray diffraction analysis revealed HCOF‐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 HCOF‐101, showcasing the potential use of HCOF‐101 for optical information storage. 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.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202109987