Inorg. Chem. 2023, 62, 31, 12501–12509.https://doi.org/10.1021/acs.inorgchem.3c01726

Organic–inorganic metal halides (OIMHs) have various crystal structures and offer excellent semiconducting properties. Here, we report three novel OIMHs, (PPA)₆InBr₉ (PPA = [C₆H₅(CH₂)₃NH₃]⁺), (PBA)₂SbBr₅, and (PBA)₂SbI₆ (PBA = [C₆H₅(CH₂)₄NH₃]⁺), showing typical zero-dimensional (0D) structure, octahedra dimers, and corner-sharing one-dimensional chains and crystallized in the monoclinic system with P2₁, P2₁/c, and C2/c space groups, respectively. (PPA)₆InBr₉, (PBA)₂SbBr₅, and (PBA)₂SbI₆ have experimental optical band gaps of ∼3.16, ∼2.24, and 1.48 eV, respectively. (PPA)₆InBr₉ exhibits bright-orange light emission centered at 642 nm with a full-width at half-maximum of 179 nm (0.51 eV) and a Stokes shift of 277 nm (1.46 eV). After Sb³⁺ doping, the peak position did not change, and the photoluminescence quantum yield increased significantly from 9.2 to 53.0%. The efficient emission of Sb:(PPA)₆InBr₉ stems from the isolated ns² luminescent center and strong electron–phonon coupling, making the spin-forbidden ³P₁–¹S₀ observable. By combining commercial blue and green phosphors with orange-red-light-emitting (PPA)₆In_0.99Sb_0.01Br₉, a white-light-emitting diode was constructed, with the color-rendering index reaching up to 92.3. Our work highlights three novel 0D OIMHs, with chemical doping of Sb³⁺ shown to significantly enhance the luminescence properties, demonstrating their potential applications in solid-state lighting.