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

Abstract By employing di-palladium complex [(bpy) 2 Pd 2 (NO 3 ) 2 ](NO 3 ) 2 (where bpy = 2, 2′-bipyridine) as corners and tetrapyrazolate calix[4]arene-based ligand ( L 4 − ) as linkers, a novel cavity-containing high-positively-charged polypyrazolate-bridged metallo-macrocycle [Pd 16 L 4 ] 16 + ·16NO 3 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 NO 3 − were trapped within the amphiphilic 3-D microporous channels in the solid state.