Antimony Dopant-Driven Monomer-Dimer Structural Transition in a Zero-Dimensional Indium Halide Hybrid

Area of Science:

• Materials Science
• Inorganic Chemistry
• Solid-State Chemistry

Background:

• Metal-ion doping in zero-dimensional (0D) metal halide hybrids typically causes minor structural changes.
• Existing research suggests doping preserves the structural and dimensional integrity of these materials.
• This work challenges the conventional understanding of doping effects in 0D metal halide hybrids.

Purpose of the Study:

• To investigate the impact of antimony (Sb³⁺) doping on the structure of a 1-methylpiperazine-based indium bromide hybrid.
• To explore the potential of dopant incorporation as a structural modulator in 0D metal halide hybrids.
• To correlate structural transformations with changes in luminescence properties.

Main Methods:

• Synthesis of antimony-doped indium bromide hybrids.
• Structural characterization using X-ray diffraction and other techniques.
• Photoluminescence spectroscopy to analyze emission properties.
• Density Functional Theory (DFT) calculations and thermodynamic formation energy analysis.

Main Results:

• Sb³⁺ doping induced a structural transition from a 0D monomeric structure to a dimeric framework.
• The doped material exhibited edge-sharing octahedral units with strong orange emission (photoluminescence quantum yield ≈59%).
• Structural modulation and luminescence were consistent across varying Sb³⁺ concentrations.
• DFT and thermodynamic analyses confirmed self-trapped exciton-mediated Sb³⁺ emission and favored the dimeric phase.

Conclusions:

• Dopant incorporation can significantly alter the overall structure and dimensionality of 0D metal halide hybrids.
• Antimony doping is a viable strategy for tuning the luminescence of these materials.
• This study establishes doping as a powerful tool for designing novel metal halide hybrid structures and optoelectronic properties.