Intermolecular Halogen and Hydrogen Bonding-Controlled Self-Assembly of Network Structures

Two kinds of tetra-dentate halogen bonding donors were synthesized by introducing tetrafluoroiodide benzene into tetraphenylene methane and tetraphenyl porphyrin modules. 3,3',5,5'-Tetramethyl-4,4'-bipyridine (TMBP) was synthesized as halogen bonding acceptor. A type of supramolecular network structure was constructed by self-assembly of tetraphenylmethane-centered halogen donor and TMBP in solid phase based on intermolecular I center dot center dot center dot N halogen bonds and H center dot center dot center dot N hydrogen bonds. The crystal structure shows that one tetrahedral halogen bonding donor binds four TMBP molecules through two sets of I center dot center dot center dot N halogen bonds and two sets of H center dot center dot center dot N hydrogen bonds, correspondingly, one TMBP molecule binds two tetrahedral molecules through one set of I center dot center dot center dot N halogen bonds and one set of H center dot center dot center dot N hydrogen bonds to form a monolayer network structure distributed with square structures with grid width of 2.37 nm. And further stacking is controlled by other hydrogen and halogen bonds between layers. The crystal data of tetradentate halogen bonding donor molecules of porphyrins show that donor molecules assemble themselves in plane controlled by more complex weak intermolecular C-I center dot center dot center dot pi and H center dot center dot center dot F interaction, and further stacking is controlled by pi-pi stacking between layers.

Automated summary

Two types of tetra-dentate halogen bonding donors were synthesized using tetrafluoroiodide benzene in tetraphenylene methane and tetraphenyl porphyrin modules. 3,3',5,5'-Tetramethyl-4,4'-bipyridine (TMBP) was used as a halogen bonding acceptor. Through self-assembly, a supramolecular network structure was formed in the solid phase based on intermolecular I···N halogen bonds and H···N hydrogen bonds. Crystal structure revealed the binding patterns of the molecules and the stacking controlled by other hydrogen and halogen bonds.