Over the years the design and construction of compartment ligands has become a fascinating investigation field of coordination chemistry since metal complexes of these ligands have been used for the generation of compounds with specific spectroscopic and magnetic properties and thus of interesting potential applications.1-3 Of the many metalloenzymes, approximately one third of all enzymatic proteins, there is a group of copper proteins which possess functionalities ranging from electron transfer to hydrocarbon oxidation in many forms of lives.
4-7Our research has focused on the synthesis of optically active metal complexes based on chiral diamine skeletons.
8,9Schiff base Robson-type macrocycles containing two bridging phenol groups have been widely used to synthesize homo-and hetero-dinuclear complexes.10,11 Typically, Robsontype macrocyclic complexes like tetraazadiphenol macrocyclic transition metal complexes have been derived from the template condensation of achiral diamines such as ethylenediamine or diethylenetriamine and 2-hydroxy-5-methylbenzene-1,3-dicarbaldehyde.10 However, the use of chiral diamines such as 1R,2R-diaminocyclohexane, 1R,2R-diphenylethylenediamine, and R-1,1-binaphthalenyl-2,2-diamine in the construction of chiral Schiff base Robson-type macrocycles has received only limited study.
12The advantages of chiral ligands are enantioselectivity in catalysis based on stereo-specific coordination geometry, thus regulating stereo-selectivity. In order to better understand some aspects of different molecular topologies, we explore in the current paper the synthesis, optical properties and crystal structures of two tetraazadiphenol macrocyclic dinuclear copper ( ]ditriacontane-2, 10,12,14,16(32),17,25,27(31),28, 30-decene-31,32-diol}. The copper(II) complex 1 was prepared by the reaction of trans-1,2-diaminocyclohexane with cupric chloride dihydrate in methanol in the presence of 2,6-diformyl-p-cresol (DFPC). When [Cu 2 ([20]-DCHDC)Cl 2 ]·6H 2 O (1) was treated with sodium bromide, as depicted in Scheme 1, the dinuclear Cu(II) bromo complex 2 was formed as pale green precipitate.
Results and DiscussionGeneral Properties. The chloro complex 1 is soluble in water, methanol, hot DMSO and hot DMF. The bromo complex 2 is soluble in hot methanol and hot DMSO. The molar conductances of complex 1 (λ M(methanol) = 65 ohm
