Synthesis of single-crystalline sp2-carbon-linked covalent organic frameworks through imine-to-olefin transformation
Shengxu Li1,2, Shunqi Xu3, En Lin4,5
1Key Laboratory of Advanced Marine Materials, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, China.
Abstract:
sp2-carbon-linked covalent organic frameworks (sp2c-COFs) are crystalline porous polymers with repeat organic units linked by sp2 carbons, and have attracted increasing interest due to their robust skeleton and tunable semiconducting properties. Single-crystalline sp2c-COFs with well-defined structures can represent an ideal platform for investigating fundamental physics properties and device performance. However, the robust olefin bonds inhibit the reversible-reaction-based crystal self-correction, thus yielding polycrystalline or amorphous polymers. Here we report an imine-to-olefin transformation strategy to form single-crystal sp2c-COFs. The isolated single crystals display rectangular nanotube-like domains with sizes up to approximately 24 μm × 0.8 μm × 0.8 μm, and permanent pore distribution around 1.1 nm. The highly conjugated olefin linkage endows the crystals with enhanced electronic connectivity which determines a remarkable room-temperature metal-free ferromagnetism (8.6 × 10-3 emu g-1). Our protocol is robust and generally applicable for the synthesis of single-crystalline sp2c-COFs for future spin-electron devices.
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