Solvent-Dependent Self-Assembly of Hydrogen-Bonded\nOrganic Porphyrinic Frameworks

Abstract

Three hydrogen-bonded organic frameworks\n(HOFs) (<b>HOF-26</b>, <b>HOF-27</b>, <b>HOF-28</b>) have been crystallized\nfrom a benzonitrile-based porphyrinic organic linker 4,4′,4″,4‴-(porphyrin-5,10,15,20-tetrayl)­tetrabenzonitrile\n(PTTBN), in ethylbenzene, nitrobenzene, and tetrahydrofuran, respectively,\nand structurally characterized. Close inspection of the crystal structure\nof the HOFs reveals that PTTBN units form a two-dimensional hydrogen-bonded\nsql network but with varied hydrogen bonding connectivities, packing\npatterns, and host–guest interactions. The pore system in these\nHOFs can be systematically modulated by the guest molecules and tuned\nfrom discrete cavities to one-dimensional channels with distinct dimensions.\nEnergy decomposition analysis was carried out to investigate the intralayer\nand interlayer interaction energy to understand the solvent-dependent\nself-assembly.