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

摘要

Synthesis, molecular and supramolecular structures, electrochemistry and magnetic properties of two diphenoxo-bridged dicopper(II) compounds [CuII 2L(H2O)(ClO4)]ClO42H2O (1) and [CuII 2L(N3)2]2H2O (2) derived from a tetraimino diphenolate macrocyclic ligand H2L, obtained on [2+2] condensation of 4-methyl-2,6-diformylphenol and 2,20-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 = JS1S2) 776 and 836 cm1 for 1 and 2, respectively.