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Reactions of [Cu(NCMe)4]+ with stoichiometric amount of diphosphine R2P–(C6H4)n–PR2, (R = NC4H4, n = 1; R = Ph, n = 1, 2, 3) or tri-phosphine 1, 3, 5-(PPh2–C6H4–)3–C6H3 ligands give the corresponding di- or trinuclear copper(I) acetonitrile-phosphine complexes 1–5. Substitution of the labile acetonitrile groups with chelating aromatic diimines – 2, 2′-bipyridine (bpy), 1, 10-phenanthroline (phen), 5, 6-dimethyl-1, 10-phenanthroline (dmp), 5, 6-dibromo-1, 10-phenanthroline (phenBr2) – gives the corresponding substituted compounds 6–16. In all complexes 1–16 each central CuI atom has tetrahedral configuration completed with two N- and two P-donor groups. The compounds obtained were characterized using elemental analysis, ESI-MS, X-ray crystallography, and NMR spectroscopy. All phosphine-diimine compounds 6–16 are photoluminescent at room temperature both in dichloromethane solution and in solid state (λex = 385 nm). In CH2Cl2 solution the maxima of emission bands are found in a range 540–640 nm, and in solid in a similar range 538–620 nm. Emission of 6–16 is assigned to the triplet excited state dominated by the charge transfer transitions with contribution of the MLCT character. |
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