Enantiopure Calcium Iminophosphonamide Complexes: Synthesis, Photoluminescence, and Catalysis

The synthesis of calcium complexes ligated by three different chiral iminophosphonamide ligands, L-H (L=[Ph₂ P{N(R)CH(CH₃ )Ph}₂ ]), L'-H (L'=[Ph₂ P{NDipp}{N(R)CH(CH₃ )Ph}]), (Dipp=2,6-ⁱ Pr₂ C₆ H₃ ), and L''-H (L''=[Ph₂ P{N(R)CH(CH₃ )naph}₂ ]), (naph=naphthyl) is presented. The resulting structures [L₂ Ca], [L'₂ Ca], and [L''₂ Ca] represent the first examples of enantiopure homoleptic calcium complexes based on this type of ligands. The calcium complexes show blue-green photoluminescence (PL) in the solid state, which is especially bright at low temperatures. Whereas the emission of [L''₂ Ca] is assigned to the fluorescence of naphthyl groups, the PL of [L₂ Ca] and [L'₂ Ca] is contributed by long-lived phosphorescence and thermally activated delayed fluorescence (TADF), with a strong variation of the PL lifetimes over the temperature range of 5-295 K. Furthermore, an excellent catalytic activity was found for these complexes in hydroboration of ketones at room temperature, although no enantioselectivity was achieved.