Rational Design of Organically Functionalized Polyoxopalladates and Their Supramolecular Properties

The Sr^II -centered 12-palladate(II) open-cube {SrPd₁₂ (OAc)₃ } has been systematically evolved by substitution of the three acetate ligands by a library of saturated carboxylic acids with increasing chain lengths leading to four novel polyoxopalladates(II) with the formula [SrPd₁₂ O₆ (OH)₃ (PhAsO₃ )₆ (L)₃ ]^4- (SrPd₁₂ L₃ , L=C_n H_2n+1 COO, n=2 to 5). These first examples of surfactant-type polyoxopalladates with a hydrophilic metal-oxo unit and three hydrophobic alkyl chains were characterized in the solid state (single-crystal XRD, FTIR, TGA), in solution (¹ H, ¹³ C NMR spectroscopy), and in the gas phase (ESI-MS). The two polyanions SrPd₁₂ L₃ with chain lengths of 5 and 6 are the first examples of polyoxopalladates that are soluble and stable in organic media. The Na salts of the amphiphilic polyoxopalladates SrPd₁₂ L₃ were shown to self-assemble into "blackberry"-type spherical supramolecular structures in dilute solutions, of which an unusual "volcano"-shaped trend of assembly size versus solvent polarity is chiefly influenced by directional hydrogen bonding interactions.