Monomer-Assembly Template-Directed Synthesis of Conjugated Porous Polymer Microtubular Bundles
For porous organic materials, the defined morphology in micrometre or larger scale is acting as an extremely important role in fully releasing their molecular-level properties in bulk phase, tuning the synergetic effects of different components and facilitating their fabrication and processing. However, the synthesis strategy towards porous organic materials with well-controlled morphologies is still very limited and full of challenges. Here, we report a simple self-templated method to construct conjugated porous polymer microtubular bundles in fused fashion. In the synthesis processes, the monomer 1,3,5-benzene-tricarbohydrazide is firstly assembled into crystalline microfiber bundles as the template, which is then condensed with 1,7-para-formylphenyl-perylene-3,4,9,10-tetracarboxylic diimide via the dynamic covalent acylhydrazon linkage. Upon a quasi-Kirkendall effect and Ostwald ripening process, a conjugated porous polymer featuring smooth microtubular bundles can be essentially constructed. Such defined hierarchical morphology exhibits the substantial co-used tubular walls and orientated channels with sub-micrometre-sized diameters and the lengths in tens of micrometers, thus rendering an extremely high accessibility of their redox active sites.