Photoluminescence Behavior of Zero-Dimensional Manganese Halide Tetrahedra Embedded in Conjugated Organic Matrices

Zero-dimensional hybrid manganese halides with the type-I band alignment between the manganese halide tetrahedra and organic matrices have attracted much attention as highly efficient narrow-band green emitters. Herein we study the photoluminescence (PL) behavior of hybrid manganese bromides with type-II band alignment, where the lowest unoccupied molecular orbital (LUMO) level can be tuned by employing quaternary phosphonium dications with different degrees of conjugation. For low-conjugated organic matrices, the band alignment can shift from type II in the ground state to type I in the excited state, which enables high photoluminescence quantum yields. In contrast, for high-conjugated organic matrices, the band alignment cannot convert to type I in the excited state because the LUMO lies too low, and thus, the excited electrons are transferred from the tetrahedra to the matrices, which leads to severe PL quenching. Our results show the importance of the excited-state band alignment for understanding the PL behavior of hybrid metal halide semiconductors.