Abstract
A new series of mononuclear copper(I) halide complexes possessing 5-tert-butyl-3-(pyrimidine-2-yl)-1H-1,2,4-triazole (bpmtzH) and PPh3, Cu(bpmtzH)(PPh3)X (X = I (1); Br (2); Cl (3)), have been synthesized and characterized. As revealed via X-ray crystallography, 1–3 show a chiral, distorted tetrahedral N2PX arrangement, in which bpmtzH is a neutral bidentate chelating ligand using the 4-N of the 1,2,4-triazolyl ring and one N donor from the 2-pyrimidyl ring, consistent with the computational results. A comparatively weak low-energy absorption tail is observed between 320 and 450 nm for CH2Cl2 solutions of 1–3 at room temperature, ascribing to charge-transfer transitions with appreciable metal-to-ligand charge transfer (MLCT) character. Complexes 1–3 in the solid state have good luminescence at ambient temperature, although they are non-emissive in solution. The solid-state emission, most likely originating from both 3MLCT and 3XLCT transitions, can be modulated via alteration of the halide bound to {Cu(bpmtzH)(PPh3)} motif.
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