Disphenoidal Zero-Dimensional Lead, Tin, and Germanium Halides: Highly Emissive Singlet and Triplet Self-Trapped Excitons and X-ray Scintillation

Low-dimensional metal halides have been researched as optoelectronic materials for the past two decades. Zero-dimensional halides of ns² elements (Sn, Pb, Sb) have recently gained attention as highly efficient broadband light emitters. These compounds comprise discrete metal halide centers, isolated by bulky organic cations. Herein, we report isostructural halide complexes of Ge(II), Sn(II), and Pb(II) with a 1-butyl-1-methyl-piperidinium cation (Bmpip), featuring unusual disphenoidal coordination with a highly stereoactive lone pair. Spectrally broad, bright emission from highly localized excitons, with quantum efficiencies of up to 75%, is observed in blue to red spectral regions for bromides (for Pb, Sn, and Ge, respectively) and extends into the near-infrared for Bmpip₂SnI₄ (peak at 730 nm). In the case of Sn(II) and Ge(II), both singlet and triplet excitonic emission bands have been observed. Furthermore, Bmpip₂SnBr₄ and Bmpip₂PbBr₄ exhibit X-ray-excited luminescence (radioluminescence) with brightness being commensurate with that of a commercial inorganic X-ray scintillator (NaI:Tl).