Hexaazatriphenylene‐Based Hydrogen‐Bonded Organic Framework with Permanent Porosity and Single‐Crystallinity

Abstract

Abstract Hydrogen‐bonded organic frameworks (HOFs) have drawn unprecedented interest because of their high crystallinity as well as facile process for construction, deconstruction, and reassembly arising from reversible bond formation‐dissociation. However, structural fragility and low stability frequently prevent formation of robust HOFs with permanent porosity. Here, we report that hexakis(4‐carboxyphenyl)‐hexaazatriphenylene ( CPHAT ) forms three dimensionally networked H‐bonded framework CPHAT‐1 . Interestingly, the activated framework CPHAT‐1 a retains not only permanent porosity but single‐crystallinity, enabling precise structural characterization and property evaluation on a single crystal. Moreover, CPHAT‐1 a retains its framework up to 339 °C or in hot water and in acidic aqueous solution. These results clearly show that even a simple H‐bonding motif can be applied for the construction of robust HOFs, which creates a pathway to establish a new class of porous organic frameworks. We also characterize its uptake of gases and I 2 , in addition to a detailed photophysical study (spectroscopy and dynamics of proton and charge transfers) of its unit in solution, and of its single crystal under fluorescence microscopy, in which we observed a marked strong anistropy and narrow distribution. The results bring new findings to the area of HOFs and their possible applications in science and technology.