Excited state energy landscape of phosphorescent group 14 complexes

Great progress has been achieved on phosphorescent or photoactive complexes of the Earth-abundant transition metals, while examples for phosphorescent heavy main group element complexes are rare, in particular for group 14 complexes in the oxidation state +II. The known compounds often show only weak phosphorescence with fast non-radiative deactivation. The underlying photophysical processes and the nature of the phosphorescent electronic states have remained essentially unexplored. The present combined photophysical and theoretical study on tin(ii) and lead(ii) complexes E(bpep) with the dianionic tridentate ligand bpep^2- (E = Sn, Pb; H₂bpep = 2-[1,1-bis(1H-pyrrol-2-yl)ethyl]pyridine) provides unprecedented insight in the excited state energy landscape of tetrel(ii) complexes. The tin complex shows green intraligand charge transfer (ILCT) phosphorescence both in solution and in the solid state. In spite of its larger heavy-atom effect, the lead complex only shows very weak red phosphorescence from a strongly distorted ligand-to-metal charge transfer (LMCT) state at low temperatures in the solid state. Detailed (TD-)DFT calculations explain these observations and delineate the major path of non-radiative deactivation via distorted LMCT states. These novel insights provide rational design principles for tetrel(ii) complexes with long-lived phosphorescence.