Structural design enables highly-efficient green emission with preferable blue light excitation from zero-dimensional manganese (II) hybrids

Manganese (II) compounds are promising luminescent candidates for white light-emitting diodes (WLEDs) applications. However, the forbidden d-d transition of Mn2+ ion makes the absorption of blue light and emission relatively weak without a sensitizer. The strategy of isolating MnXn (X is the ligand) with some ionic liquids is used to design two new hybrid compounds in this study, focusing on the orbital hybridization to relax the parity selection rule of the d-d transition. A large hindrance of the organic cations in the two new Manganese (II) hybrids enables a large Mn-Mn distance (up to ~ 10 Å) to form zero-dimensional (0D) structures, and the Mn sites in both compounds have a low site symmetry (C2 or C1). The 0D structure of MnXn polyhedral is beneficial to isolatedly investigate the orbital hybridization of the ligand and Mn2+ ion. A higher orbital hybridization extent for Mn-Br bond is evidenced by Density Functional Theory (DFT) simulation. This conclusion leads to the strong and stable green light emissions under preferable blue light (460 nm) excitations, giving photoluminescence quantum yields (PLQYs) as high as 76%. The WLEDs fabricated with these compounds have presented high luminous efficiency up to ~130 lm/W and survived multiple stability tests. The research favors the discovery of ideal Mn compounds for displays and lighting applications.