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Upon interaction with amine and alcohol guests, Zn-Zn and Zn-2H ethane-bridged bis-porphyrin hosts undergo dramatic conformational switching from a syn to an anti form. The thermodynamic parameters obtained exhibit excellent linear enthalpy-entropy correlations, which are distinctly different for amines and alcohols but essentially independent of the host structure. Analyses of the compensation plots reveal a more rigid complex structure and more extensive desolvation upon complexation with amines than for alcohols, which may be ascribed to the different nucleophilicity, binding strength, solvation and geometry.