Adaptive Fabrication of Porous Crystals through Multiple-Site Noncovalent Conjunction of [1,4]Diazocine-Embedded Three-Dimensionally Concave Nanographenes

Noncovalent porous crystals with superior processability have recently received intense attention due to their vast emerging applications. However, the construction of such materials is still extremely incidental and lacks a fine control. Herein, we develop a unique strategy using three-dimensional nanographenes with tunable bulky configurations to adaptively fabricate a series of noncovalent porous crystals. Stereospecific nanographenes with either unilateral or bilateral curved [1,4]diazocine domains are obtained by Scholl cyclization of tetracarbazole precursors bearing diverse substituents. Leveraging the multiple intrinsic concavities variably constructed by the rigid octagons and flexible carbazole groups, these nanographenes readily self-assemble into noncovalent porous crystals featuring straight one-dimensional, zigzag one-dimensional, or interconnected two-dimensional channels. Interestingly, coassembly with other aromatic derivatives such as pyrene further facilitates the construction of porous cocrystals from porosity-absent building blocks. Moreover, upon coassembly with fullerenes, the long-range charge-transfer interactions endow the resulting porous cocrystals with conducting properties.