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

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Doping metal halide hybrids with antimony (Sb3+) ions transforms their structure from zero-dimensional (0D) to dimeric frameworks. This doping strategy effectively tunes luminescence properties in these advanced materials.

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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.