In-Depth Study of the Electronic Properties of NIR-Emissive _κ3N Terpyridine Rhenium(I) Dicarbonyl Complexes

The structure–properties relationship in a series of carbonyl rhenium(I) complexes based on substituted terpyridine ligands of general formula [Re(κ^xN-Rtpy)(CO)_yL]ⁿ⁺ is explored by both experimental and theoretical methods. In these compounds, the terpyridine ligands adopt both bidentate (κ²N) and terdentate (κ^3N) coordination modes associated with three or two carbonyls, respectively. Conversion from the κ²N to the κ³N coordination mode leads to large changes in the absorption spectra and oxidation potentials due to destabilization of the HOMO level of each complex. The absorption profiles of the κ³N complexes cover the whole visible spectra with lower maxima around 700 nm, tailing out to 800 nm, while no emission is observed with Br^– as the axial ligand L. When the axial ligand is modified from the native halide to pyridine or triphenylphosphine, the lowest absorption band is blue-shifted by 60 and 90 nm, respectively. These cationic complexes are near-infrared emitters with emission maxima between 840 and 950 nm for the pyridine compounds and 780–800 nm for the triphenylphosphine compounds.