Hydrosoluble Cu(i)-DAPTA complexes: Synthesis, characterization, luminescence thermochromism and catalytic activity for microwave-assisted three-component azide-alkyne cycloaddition click reaction

New hydrosoluble and air-stable Cu(i) halide compounds, viz. [CuX(DAPTA)₃] (1) and (2), and [Cu(μ-X)(DAPTA)₂]₂ (3) and (4) (X = Br or I, in this order), have been prepared by reacting Cu(i) halide (i.e., bromide or iodide) with 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) under mild conditions. They represent the first examples of Cu(i) halide complexes bearing the DAPTA ligand, which have been fully characterized by elemental analysis, IR, ¹H, ¹³C{¹H} and ³¹P{¹H} NMR spectroscopies, ESI-MS⁺ and, for 4, also by single-crystal X-ray diffraction (SCXRD) analyses. Complexes 1-4 are efficient catalysts for the one-pot microwave assisted three-component (terminal alkyne, organic halide and NaN₃) Huisgen cycloaddition reaction in aqueous media to afford the corresponding disubstituted triazoles. The catalysis proceeds with a broad alkyne substrate scope and according to "click rules". Photophysical studies of compound 4 showed an unusual reversible thermochromic behaviour exhibiting a blue emission at 298 K due to the halide-to-ligand charge transfer (³XLCT) and a red emission at 77 K because of the {Cu₂I₂} unit.