Abstract
When the ligand 1,4,5-triazanaphthalene (abbreviated as tan) is reacted with Cu(II) BF4- and ClO4- salts, a variety of mononuclear compounds has been found, all with the [Cu(tan)(4)] unit and varying amounts of weakly coordinating axial ligands and lattice solvents. Reproducible compounds formed include two purple compounds, analyzing as [Cu(tan)(4)](ClO4)(2)(CH3OH)(2)(H2O) (1) and [Cu(tan)(4)] (BF4)(2)(CH3OH)(1.5)(H2O) (3), and two blue compounds, analyzing as [Cu(tan)(4)](ClO4)(2)(H2O)(2) (2) and [Cu(tan)(4)](2)(BF4)(2)(H2O)(2) (4). Upon standing at room temperature, red-coloured, mixed-valence dinuclear-based 3D coordination polymers are formed by conversion of the purple/blue products, of which [Cu-2(tan)(4)](n)(BF4)(3n) (5) and the isomorphic methanol-water adduct [Cu(tan)(4)](n)(BF4)(3n)(CH3OH)(n)(H2O)(5n) (5A) are presented in this paper. In addition a fully reduced dinuclear Cu(I) compound of formula [Cu-2(tan)(3)(ClO4)(2)] (7) has been observed, and structurally characterized, as a rare three-blade propeller structure, with a Cu-Cu distance of 2.504 angstrom.