Host-Guest Complexation of Bisporphyrin Cleft and Electron-Deficient Aromatic Guests.

The host-guest complexation of a bisporphyrin cleft with various electron-deficient guest molecules was studied in solution and in the solid-state. X-ray crystal structures of a bisporphyrin cleft with naphthalene dianhydride and 2,4,7-trinitrofluorenone reveal that these guest molecules were located within the bisporphyrin cleft and formed ideal π-π stacking interactions in a host-guest ratio of 1:1. Isothermal titration calorimetry determined the binding constants and thermodynamic parameters for the 1:1 host-guest complexations in 1,2-dichloroethane and toluene. Two types of enthalpy-entropy compensation effects were found: (1) The tightly stacked host-guest structures restrict guest movement within the cleft, which results in significant desolvation with large intrinsic entropies. (2) The loosely bound guests maintain their molecular freedom within the bisporphyrin cleft, which leads to less desolvation with small intrinsic entropies. Chiral guest encapsulation directed the clockwise and anticlockwise twisted conformations of the bisporphyrin units, which induced bisignate CDs.