Synthesis, molecular and supramolecular structures, electrochemistry and magnetic properties of two macrocyclic dicopper(II) complexes: Microporous supramolecular assembly

Abstract

Synthesis, molecular and supramolecular structures, electrochemistry and magnetic properties of two diphenoxo-bridged dicopper(II) compounds [Cu II 2L(H 2O)(ClO 4)]·ClO 4·2H 2O ( 1) and [Cu II 2L(N 3) 2]·2H 2O ( 2) derived from a tetraimino diphenolate macrocyclic ligand H 2L, obtained on [2+2] condensation of 4-methyl-2,6-diformylphenol and 2,2′-dimethyl-1,3-diaminopropane, are presented. Supramolecular structure of both 1 and 2 are three-dimensional resulting from hydrogen bonding interactions. Interestingly, the 3-D self-assembly of 2 contains micropores having the dimension of 0.35 nm. Electrochemical analyses reveal that both of these compounds exhibit two-step couples in the reduction window. Variable-temperature (2–300 K) magnetic susceptibilities measurements of the two compounds reveal that the metal centers in both of the complexes are coupled by strong antiferromagnetic interactions with J values ( H = − J S 1 · S 2 ) −776 and −836 cm −1 for 1 and 2, respectively.