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While metal doping strategies have proven effective in regulating the bandgap and enhancing the photophysical properties of hybrid metal halides, site-specific atom alloying by mixing metals of different elements offers a new route for material modification. Here an antimony halide hybrid material with the formula of (C₄H₁₂N₂)₅(SbCl₅)₂(SbCl₆)Cl₄ (Py-SbCl) is shown with crystallographically independent alternating square pyramidal SbCl₅ and octahedral SbCl₆ sites sandwiched by organic layers. Interestingly, the octahedral site of the SbCl₆ can be fully replaced by the In3+ ions, forming the alloyed compound (C₄H₁₂N₂)₅(SbCl₅)₂(InCl₆)Cl₄ (Py-SbInCl). More importantly, the latter shows a near-unity photoluminescence quantum yield of 97%, which is ≈7 times of enhancement compared to the pristine Py-SbCl compound. This is mainly due to the much-enhanced Young's modulus, higher radiative decay rates and longer electron transient rates, presumably stemming from shorter In─Cl bond distances and higher dipole moments, as revealed by a cocktail study of X-ray single-crystal crystallography, density functional theory, femtosecond transient absorption spectroscopy and so on. In addition, it is shown that Py-SbInCl is an excellent yellow phosphor that can be used for white light-emitting diodes and other applications such as counterfeiting. Therefore, making site-specific alloying compounds may open a new design approach for functional bimetallic hybrid materials.
Ahmad et al. (Mon,) studied this question.