Hydrogen-bonded porous organic crystals are promising candidates for functional organic materials due to their easy construction and flexibility arising from reversible bond formation-dissociation. However, it still remains challenging to form porous materials with void spaces that are well-controlled in size, shape, and multiplicity because even well-designed porous frameworks often fail to generate pores within the crystal due to unexpected disruption of hydrogen bonding networks or interpenetration of the frameworks. Herein, we demonstrate that a series of C3-symmetric π-conjugated planar molecules (Tp, T12, T18, and Ex) with three 4,4'-dicarboxy-o-terphenyl moieties in their periphery can form robust hydrogen-bonded hexagonal networks (H-HexNets) with dual or triple pores and that the H-HexNets stack without interpenetration to yield a layered assembly of H-HexNet (LA-H-HexNet) with accessible volumes up to 59%. Specifically, LA-H-HexNets of Tp and T12 exhibit high crystallinity and permanent porosity after desolvation (activation): SABET = 788 and 557 m(2) g(-1), respectively, based on CO2 sorption at 195 K. We believe that the present design principle can be applied to construct a wide range of two-dimensional noncovalent organic frameworks (2D-nCOFs) and create a pathway to the development of a new class of highly porous functional materials.

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 , 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.

Generation of four polymorphs of 2D-nCOF crystals that are formed through stacking of a hydrogen-bonded, hexagonally-networked framework is revealed for the first time. The structural diversity is caused not from the topology or the stacking manner of the framework but from subtle structural factors such as rotational conformation and location of conformational frustration within the framework.