Tetrapyrazolyl-calix[4]arene-based supramolecular architectures from [Pd16L4] macrocycle to three-dimensional microporous channels

By employing di-palladium complex [(bpy)2Pd2(NO3)2](NO3)2 (where bpy = 2, 2′-bipyridine) as corners and tetrapyrazolate calix[4]arene-based ligand (L4 −) as linkers, a novel cavity-containing high-positively-charged polypyrazolate-bridged metallo-macrocycle [Pd16L4]16 +·16NO3 with Pd(II)⋯Pd(II) dimetal-coordination motifs has been synthesized by a directed coordination driven self-assembly with spontaneous deprotonation of the 1H-bipyrazole ligands in aqueous solution. The counter ions NO3− were trapped within the amphiphilic 3-D microporous channels in the solid state.