Control of Crystallinity and Porosity of Covalent Organic Frameworks by Managing Interlayer Interactions Based on Self-Complementary π-Electronic Force
Control of Crystallinity and Porosity of Covalent Organic Frameworks by Managing Interlayer Interactions Based on Self-Complementary π-Electronic Force
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DOI：
10.1021/ja3100319
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发表时间：
2013-01-16
影响因子：
15
通讯作者：
Jiang, Donglin
中科院分区：
文献类型：
--
作者：
Chen, Xiong;Addicoat, Matthew;Jiang, Donglin
结晶度和孔隙率对于结晶多孔共价有机框架（COF）至关重要。在这里，我们报告了通过基于自互补π电子力管理层间相互作用来综合控制COF的结晶度和孔隙率。不同摩尔比的氟取代和非取代芳族单元被集成到边缘单元中，这些单元堆叠以触发COF中的自互补π电子相互作用。这种相互作用通过最大化总晶体堆积能和最小化晶胞尺寸来提高结晶度并增强孔隙率。因此，由等摩尔量的氟取代和未取代单元组成的COF表现出最大的效果。这些结果提出了一种通过管理层间相互作用来设计 COF 的新方法。
Crystallinity and porosity are crucial for crystalline porous covalent organic frameworks (COFs). Here we report synthetic control over the crystallinity and porosity of COFs by managing interlayer interactions based on self-complementary pi-electronic forces. Fluoro-substituted and nonsubstituted aromatic units at different molar ratios were integrated into the edge units that stack to trigger self-complementary pi-electronic interactions in the COFs. The interactions improve the crystallinity and enhance the porosity by maximizing the total crystal stacking energy and minimizing the unit cell size. Consequently, the COF consisting of equimolar amounts of fluoro-substituted and nonsubstituted units showed the largest effect. These results suggest a new approach to the design of COFs by managing the interlayer interactions.