Department of Chemistry, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon, Hong Kong, China.
Chem Commun (Camb). 2018 Aug 21;54(68):9470-9473. doi: 10.1039/c8cc05225e.
We employ a two-step strategy for accessing crystalline porous covalent networks of highly conjugated π-electron systems. For this, we first assembled a crystalline metal-organic framework (MOF) precursor based on Zr(iv) ions and a linear dicarboxyl linker molecule featuring backfolded, highly unsaturated alkyne backbones; massive thermocyclization of the organic linkers was then triggered to install highly conjugated, fused-aromatic bridges throughout the MOF scaffold while preserving the crystalline order. The formation of cyclized carbon links not only greatly strengthens the precursor coordination scaffold, but also, more importantly, enhances electroactivity and charge transport throughout the polycyclic aromatic grid.
我们采用两步策略来构建高度共轭π电子体系的结晶多孔共价网络。为此，我们首先组装了一种基于 Zr(iv)离子和具有折叠、高度不饱和炔烃骨架的线性二羧酸连接分子的结晶金属有机骨架（MOF）前体；然后大量热环化有机连接体，在整个 MOF 支架中安装高度共轭的、融合的芳构桥，同时保持结晶有序。环化碳键的形成不仅极大地增强了前体配位支架的稳定性，而且更重要的是增强了整个多环芳烃网格的电活性和电荷输运能力。
