The photophysical tuning is reported for a series of tetraphenylphosphonium (TPP) metal halide hybrids containing distinct metal halides, TPP2MX
Mechanochemical synthesis has emerged as a facile method for the preparation of a wide range of organic, inorganic, and polymeric materials. Here, we report the use of mechanochemical synthesis for the preparation of ionically bonded organic metal halide hybrids with a zero‐dimensional (0D) structure at the molecular level. (Ph4P)2SbCl5and (Ph4P)2MnCl4were synthesized by grinding appropriate ratios of organic halide salt Ph4PCl with inorganic metal halide salts SbCl3and MnCl2, respectively. The structural and photophysical properties of mechanochemically synthesized (Ph4P)2SbCl5and (Ph4P)2MnCl4were characterized, which are almost identical to those of single crystals prepared by slow solution growth. By reacting Ph4PCl with both SbCl3and MnCl2, we have been able to produce a mixture of two 0D organic metal halide hybrids that exhibit a dual emission covering a wide range of the spectrum with Commission Internationale de l'Eclairage (CIE) coordinates of (0.4898, 0.4800). Our work has clearly established mechanochemical synthesis as an effective method to produce ionically bonded organic‐inorganic hybrids.
more » « less- NSF-PAR ID:
- 10231916
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- ChemPhotoChem
- Volume:
- 5
- Issue:
- 4
- ISSN:
- 2367-0932
- Page Range / eLocation ID:
- p. 326-329
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract n (MXn =SbCl5, MnCl4, ZnCl4, ZnCl2Br2, ZnBr4), from efficient phosphorescence to ultralong afterglow. The afterglow properties of TPP+cations could be suspended for the hybrids containing low band gap emissive metal halide species, such as SbCl52−and MnCl42−, but significantly enhanced for the hybrids containing wide band gap non‐emissive ZnCl42−. Structural and photophysical studies reveal that the enhanced afterglow is attributed to stronger π–π stacking and intermolecular electronic coupling between TPP+cations in TPP2ZnCl4than in the pristine organic ionic compound TPPCl. Moreover, the afterglow in TPP2ZnX4can be tuned by controlling the halide composition, with the change from Cl to Br resulting in a shorter afterglow due to the heavy atom effect. -
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Abstract The photophysical tuning is reported for a series of tetraphenylphosphonium (TPP) metal halide hybrids containing distinct metal halides, TPP2MX
n (MXn =SbCl5, MnCl4, ZnCl4, ZnCl2Br2, ZnBr4), from efficient phosphorescence to ultralong afterglow. The afterglow properties of TPP+cations could be suspended for the hybrids containing low band gap emissive metal halide species, such as SbCl52−and MnCl42−, but significantly enhanced for the hybrids containing wide band gap non‐emissive ZnCl42−. Structural and photophysical studies reveal that the enhanced afterglow is attributed to stronger π–π stacking and intermolecular electronic coupling between TPP+cations in TPP2ZnCl4than in the pristine organic ionic compound TPPCl. Moreover, the afterglow in TPP2ZnX4can be tuned by controlling the halide composition, with the change from Cl to Br resulting in a shorter afterglow due to the heavy atom effect. -
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Abstract Low‐dimensional (low‐D) organic metal halide hybrids (OMHHs) have emerged as fascinating candidates for optoelectronics due to their integrated properties from both organic and inorganic components. However, for most of low‐D OMHHs, especially the zero‐D (0D) compounds, the inferior electronic coupling between organic ligands and inorganic metal halides prevents efficient charge transfer at the hybrid interfaces and thus limits their further tunability of optical and electronic properties. Here, using pressure to regulate the interfacial interactions, efficient charge transfer from organic ligands to metal halides is achieved, which leads to a near‐unity photoluminescence quantum yield (PLQY) at around 6.0 GPa in a 0D OMHH, [(C6H5)4P]2SbCl5.
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Abstract Low‐dimensional (low‐D) organic metal halide hybrids (OMHHs) have emerged as fascinating candidates for optoelectronics due to their integrated properties from both organic and inorganic components. However, for most of low‐D OMHHs, especially the zero‐D (0D) compounds, the inferior electronic coupling between organic ligands and inorganic metal halides prevents efficient charge transfer at the hybrid interfaces and thus limits their further tunability of optical and electronic properties. Here, using pressure to regulate the interfacial interactions, efficient charge transfer from organic ligands to metal halides is achieved, which leads to a near‐unity photoluminescence quantum yield (PLQY) at around 6.0 GPa in a 0D OMHH, [(C6H5)4P]2SbCl5.
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