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Modulation of a supramolecular bowl and pot by changing solvent systems and/or metal/ligand ratios.

A resorcin[4]arene-based ligand 2 a with four pyrimidine substituents at the upper rim was synthesized, and the generation of different metal-mediated superstructures from the same ligand and metal ions utilizing the unfavorable incorporation of the third and fourth Pd(II) ions to ligand 2 a was investigated. The supramolecular bowl 3 a, which comes from a 1:2 combination of ligand 2 a and [Pd(en)(NO(3))(2)], was obtained in water even though excess of Pd(II) complexes were employed. By adding methanol, the supramolecular pot 4 gradually formed, which was the major product when the ratio of mixed solvent reached methanol/water=5:1 (v/v). Host-guest complexation phenomena of 3 a toward several aromatic carboxylates were demonstrated by isothermal titration calorimetry (ITC) and by (1)H NMR spectroscopy; both the enthalpy gain from electrostatic and hydrophobic interactions, and the entropy gain from desolvation cooperatively contribute to the binding of anionically charged guests. The crystal structure of supramolecular pot 4 shows direct evidence for the hydrogen bonding between water and the aromatic pi electrons in the solid state. The modulation between supramolecular bowl 3 a and pot 4 was also made possible by changing the metal/ligand ratios in aqueous methanol solution as well as by varying the water content of the mixed solvent.