Steering the Host Network from Cage to Channel by π•••π Interactions among the Guest Molecules

2,4,6-Tris(4-bromophenoxy)-1,3,5-triazine (BrPOT) preferably forms a cage type of structure with guest molecules of hexamethylbenzene (HMB) or hexafluorobenzene (HFB) individually. However, when both guests are present simultaneously, strong pi center dot center dot center dot pi stacking interactions between the pi electron-rich HMB and pi - electron-deficient HFB guest molecules force the host molecules to assemble in a channel structure to include the pi center dot center dot center dot pi stacked guest molecules inside the channel. Picric acid (PA) and 1,3,5-trinitrobenzene (TNB) form charge transfer complexes with HMB inside the channel, and the nature of these charge transfer complexes are different from that of the binary complexes of HMB-PA or HMB-TNB. All three guest molecules, HMB, PA, and TNB, have been simultaneously included in the channel lattice of BrPOT to produce a quaternary complex.