The Re(I) coordination chemistry of a series of pyrido[2,3-b]pyrazine-derived ligands: Syntheses, characterisation and crystal structures

Reaction of 2,3-diaminopyridine with one equivalent of a functionalised vicinal diketone, in ethanol, yields a series of ligands based upon the pyrido[2,3-b]pyrazine core. The ligands were characterised by 1H, 13C–{1H} NMR, MS and UV–Vis spectroscopy. Reaction of the ligands with one equivalent of {ReBr(CO)5} gave a series of Re-Ln complexes based upon the general formula fac-{ReBr(CO)3(L)} (where L = pyrido[2,3-b]pyrazine-derived ligands, L1–L6). Solution IR studies confirmed the retention of the facially capped, tri-carbonyl coordination geometry at rhenium, and 1H NMR studies confirmed coordination of the ligand to Re(I). EI HR MS data were obtained for each complex confirming the proposed formulation and stoichiometry. Single crystal X-ray structures were obtained for three of the complexes (Re-L1, Re-L2, Re-L6), with each demonstrating that the ligands coordinate to Re(I) in a bidentate manner, via a four-membered chelate ring, which was unsymmetrical in the former two cases. The electronic absorption spectra of the complexes showed absorption into the visible region ca. 375–500 nm, (the complexes are orange-red in appearance). Following irradiation at 350–450 nm, the complexes display a solid-state broad emission peaking between 600–700 nm. The complexes were not sufficiently luminescent in solution to allow further investigation into the origin of this emission band, although with reference to related 1,8-naphthyridine complexes of Re(I) it is likely to incorporate significant 3MLCT character.

A general high yielding synthesis is reported for a series of pyrido[2,3-b]pyrazine-derived ligands together with their coordination chemistry with Re(I). Structural studies on the resultant complexes reveal a bidentate coordination mode for the ligands and spectroscopic analyses show that these complexes possess visible luminescence in the solid-state following excitation at 400–450 nm.Figure optionsDownload as PowerPoint slide