Solvent-Dependent Self-Assembly of Hydrogen-Bonded Organic Porphyrinic Frameworks

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