A C₃‐Symmetric Macrocycle‐Based, Hydrogen‐Bonded, Multiporous Hexagonal Network as a Motif of Porous Molecular Crystals

Abstract

A C 3 -symmetric p-conjugated macrocycle combined with an appropriate hydrogen bonding module (phenylene triangle) allowed the construction of crystalline supramolecular frameworks with a cavity volume of up to 58 %. The frameworks were obtained through non-interpenetrated stacking of a hexagonal sheet possessing three kinds of pores with different sizes and shapes. The activated porous material absorbed CO 2 up to 96 cm 3 g À1 at 195 K under 1 atm.

Hydrogen-bonded porous frameworks constructed by rigid π-conjugated molecules with carboxy groups

“…4d,f) [91]. This structural changes caused by the solvent insertion can change stacking manners of the H-NexNets as observed in the case of T18 [91].…”

“…The frustrated dimer is sometimes trapped by a polar molecule used as a solvent for crystallization, such as DMF, and fractured to form the "truncated catemer" type dimer, to release the frustration (Fig. 4d,f) [91]. This structural changes caused by the solvent insertion can change stacking manners of the H-NexNets as observed in the case of T18 [91].…”

“…In this hypothesis, the key motif is a H-bonded triangular porous motif formed by the peripheral three o-bis(4carboxyphenyl)benzene moieties. Although the motif has already been observed in Kobayashi's framework [74], we noticed its importance on constructing HOFs and named the motif as phenylene triangle (PhT) motif [91]. The ring size of PhT motif is appropriate to retain the network structure within crystals.…”

“…3a). That is that C 3 -symmetric π-conjugated planar building blocks (C 3 PIs) possessing three o-bis(4-carboxyphenyl)benzene moieties in periphery can form an isostructural H-bonded hexagonal network (H-HexNet) sheet via H-bonding dimerization of the carboxy groups, and that the H-HexNets are stacked to give porous layered assembly of HexNets (LA-H-HexNets) [91]. In this hypothesis, the key motif is a H-bonded triangular porous motif formed by the peripheral three o-bis(4carboxyphenyl)benzene moieties.…”

“…d PhT with one fractured dimer by insertion of a DMF molecule. Crystal structures of e frustrated and f fractured PhT observed in crystals of T18[91]…”