DFT study of guest-responsive cooperative effects: Inclusion complexation of alcohols with calix[4]pyrrole

Herein, we report guest-responsive structural changes and cooperative effects in inclusion complexes of meso-octamethylcalix[4]pyrrole. A series of lower alcohol guests were modeled using the density functional theory at B97D/6-311 + G* and ωB97D/6-311 + G* level of approximation to study their thermochemical properties and complexation geometries. Results of binding energies of CP:1-alcohol and CP:2-alcohol complexes indicated that the methylene glycol exhibited strongest binding, whereas ethane-1,2-diol has the highest cooperative effects. Attempts were also made to address the cooperative effects by correlating them with the partial charges (Hirshfeld, Atomic Dipole Corrected Hirshfeld) and the second-order energy interactions. Graphical abstract:

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