A Vanadium(III) Complex with Blue and NIR-II Spin-Flip Luminescence in Solution

Abstract

Luminescence from Earth-abundant metal ions in solution at room temperature is a very challenging objective due to the intrinsically weak ligand field splitting of first-row transition metal ions, which leads to efficient nonradiative deactivation via metal-centered states. Only a handful of 3d^<i>n</i> metal complexes (<i>n</i> ≠ 10) show sizable luminescence at room temperature. Luminescence in the near-infrared spectral region is even more difficult to achieve as further nonradiative pathways come into play. No Earth-abundant first-row transition metal complexes have displayed emission >1000 nm at room temperature in solution up to now. Here, we report the vanadium(III) complex <i>mer</i>-[V(ddpd)₂][PF₆]₃ yielding phosphorescence around 1100 nm in valeronitrile glass at 77 K as well as at room temperature in acetonitrile with 1.8 × 10^-4% quantum yield (ddpd = <i>N</i>,<i>N</i>'-dimethyl-<i>N</i>,<i>N</i>'-dipyridine-2-ylpyridine-2,6-diamine). In addition, <i>mer</i>-[V(ddpd)₂][PF₆]₃ shows very strong blue fluorescence with 2% quantum yield in acetonitrile at room temperature. Our comprehensive study demonstrates that vanadium(III) complexes with d² electron configuration constitute a new class of blue and NIR-II luminophores, which complement the classical established complexes of expensive precious metals and rare-earth elements.