Abstract
The polynuclear complexes [Mo3O8(tidf)]·dmso·2H2O (1) and [{Cu2(tidf)}2(μ-Mo8O24)] (2) (tidf2−is a symmetrical tetraiminodiphenolate Robson-type macrocyclic ligand) were prepared from equimolar combinations of [Mg2(tidf)](NO3)2·4H2O, [MoO2Cl2(dmso)2] (for1) and complex1and Cu(ClO4)2·4H2O (for2) in acetonitrile. Molecular structures of both complexes were determined and showed atypical modes of coordination. A significant observation was the remarkable flexibility of the macrocycle ligand that effectively accommodated the steric demands of metal cations and the packing forces and showed a unique mode of coordination. Spectroscopic (UV-vis and FTIR) and redox properties are discussed.
Highlights
This work is related to the current interest in searching for multimetallic complexes based on symmetric macrocycles, especially heterometallic ones
We started this project in an attempt to find a route to the synthesis of heterometallic macrocyclic complexes using our previous knowledge about the coordination chemistry of the tetraiminodiphenolate macrocyclic ligand, Transmittance (%) 1656 1533
It is well known that transmetalation reactions favor the formation of homometallic compounds, especially with symmetric ligands in the presence of labile first-row transition metal ions [1, 28,29,30,31,32]
Summary
This work is related to the current interest in searching for multimetallic complexes based on symmetric macrocycles, especially heterometallic ones. Symmetrical tetraiminodiphenolate Robson-type macrocyclic ligands, obtained by condensation of 2,6-diformyl-4methylphenol and diamines, have been extensively investigated over the years and preparation usually is achieved by template and transmetallation reactions [12,13,14]. Their related heterodinuclear complexes appear in limited number in the literature [15,16,17,18]. Preparation of heteronuclear complexes can be difficult because labile metal ions may swap positions by an intramolecular mechanism and this metal scrambling leads to mixtures of products. Thermodynamics drives the process making it difficult to control metal ion composition at the molecular level
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