Alkali metal complexes of an enantiopure iminophosphonamide ligand with bright delayed fluorescence

The enantiomerically pure ligand P,P-diphenyl-N,N'-bis((R)-1-phenylethyl)phosphinimidic amide (1; (R)-HPEPIA) was synthesized and subsequently deprotonated with alkali metal precursors to yield dimeric complexes [M-2{(R)-PEPIA}(2)] (M = Li (2), Na (3), K (4), Rb (5)). The cesium compound [M{(R)-PEPIA}] (6) crystallized as a cocrystal composed of dimeric ([Cs-2{(R)-PEPIA}(2)] (6(d)) and 1D-polymeric ([Cs{(R)-PEPIA}] (n)) (6(p)) species in a 1 : 1 ratio. The coordination polymer 6(p) features a unique sinus-shaped configuration of repeating -Cs-N-P-N-Cs-N-P-N- units. Unusual photoluminescence (PL) properties were found for solid 1-6: in contrast to the fluorescent ligand 1, the alkali metal complexes show phosphorescence at low temperatures (<100 K) and thermally activated delayed fluorescence (TADF) above similar to 150 K. The latter provides for PL quantum yields up to 36% (3) at ambient temperature. DFT calculations support that both 1 and 2-6(d) have similar singlet and triplet excited states with energy separations of a few tens of meV. The strongly enhanced intersystem crossing (ISC) in the metal complexes, resulting in TADF, is attributed to their dimeric structure. This suggests that the fluorophore dimerization may serve as a tool to effect ISC for the design of TADF emitters.