Luminescent hybrid halides with various centering metal cations (Zn, Cd and Pb) and diverse structures

Abstract

Organic–inorganic hybrid metal halides have been extensively studied because of their great potential in optoelectronics. Herein, we report three hybrid metal halides (Bmpip)₂ZnBr₄, (Bmpip)₂CdBr₄, and (Bmpip)₈Pb₁₁Br₃₀ (where Bmpip⁺ is 1-butyl-1-methyl-piperidinium, C₁₀H₂₂N⁺). (Bmpip)₂ZnBr₄ and (Bmpip)₂CdBr₄ crystallize in the P2₁/c space group with zero-dimensional crystal structures with [MBr₄]²⁻ (M = Zn, Cd) tetrahedra isolated by Bmpip⁺. (Bmpip)₈Pb₁₁Br₃₀ crystallizes in the triclinic space group P with one-dimensional corrugated chains constructed from face-sharing [PbBr₆]⁴⁻ octahedra. All of the compounds exhibit excellent ambient and thermal stability. Under UV excitation, all three compounds exhibit very broad emissions. Temperature-dependent photoluminescence measurements indicate that the broad emissions of (Bmpip)₂ZnBr₄ and (Bmpip)₂CdBr₄ can be attributed to both the organic cations and self-trapped excitons (STEs) and that the emission of (Bmpip)₈Pb₁₁Br₃₀ is assigned to STEs. Density functional theory calculations reveal that the three compounds adopt a direct band gap. This work enriches our understanding of the structure types of hybrid metal halides while revealing their diverse emission mechanisms.