Mechanochemical Synthesis of Zero Dimensional Organic‐Inorganic Metal Halide Hybrids

Abstract

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)2SbCl5 and (Ph4P)2MnCl4 were synthesized by grinding appropriate ratios of organic halide salt Ph4PCl with inorganic metal halide salts SbCl3 and MnCl2, respectively. The structural and photophysical properties of mechanochemically synthesized (Ph4P)2SbCl5 and (Ph4P)2MnCl4 were characterized, which are almost identical to those of single crystals prepared by slow solution growth. By reacting Ph4PCl with both SbCl3 and 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.

Quasi-Zero Dimensional Halide Perovskite Derivates: Synthesis, Status, and Opportunity

“…Additionally, they grew (C 9 NH 20 ) 2 SbCl 5 single crystals by using acetone as anti-solvent and DMF precursor solutions. (Ph 4 P) 2 MnCl 4 single crystals were prepared by the same group by diffusing diethyl ether into the DMF precursor solutions (Ben-Akacha et al, 2020). Likewise, other organic-inorganic 0D HPds, containing Bzmim (1-benzyl-3-methylimidazolium), such as (Bzmim) 2 SbCl 5 (Wang et al, 2019b), (Bzmim) 3 SbCl 6 (Wang et al, 2019b), (C 9 NH 20 ) 2 SnBr 4 (Zhou et al, 2018b), (PPN) 2 SbCl 5 (He et al, 2020) and (C 38 H 34 P 2 )MnBr 4 (Xu L. J. et al, 2020) single crystals (in millimetre to centimetre size scale) could be synthesized in the presence of anti-solvent (Bzmim) 2 SbCl 5 (Wang et al, 2019b) and (Bzmim) 3 SbCl 6 (Wang et al, 2019b) were also synthesized by the temperature lowering method.…”

“…Mechanochemical reactions are induced by mechanical energy input by grinding or milling of two or more solid reactants (James et al, 2012). They have many benefits, including great simplicity, economic and environmental friendliness, when compared to other methods (Ben-Akacha et al, 2020). This method may also be advantageous from a thermodynamic perspective as the solidstate reaction's driving force is more significant than the solutionbased one due to the higher chemical potential in solid-state.…”

0D Organic Manganese(II) Bromide Hybrids as Stable and Efficient X‐Ray Scintillator

“…This value is higher than that of other reported 0D Mn‐based hybrids, such as 60.7% for (1‐C 5 H 14 N 2 ) 2 MnBr 4 [ 30 ] and 30% for (Ph 4 P) 2 MnCl 4 . [ 32 ]…”

“…This value is higher than that of other reported 0D Mn-based hybrids, such as 60.7% for (1-C 5 H 14 N 2 ) 2 MnBr 4 [30] and 30% for (Ph 4 P) 2 MnCl 4 . [32] The scintillation performance of (C 40 H 38 P 2 )MnBr 4 single crystal under X-ray excitation was then systematically studied. after X-ray cutoff one order of magnitude lower than that of CsI:Tl, and even comparable to that of BGO.…”

Dramatically Enhanced X-ray Scintillation of BODIPY via Sensitization by an Organic Metal Halide

“… Photophysical characterizations found that these (C 24 H 20 P) 2 MnBr 4 powders exhibit strong green emission that peaks at 517 nm with a full width at half-maximum (fwhm) of 50 nm (Figure b and Figure S4), a high photoluminescence quantum yield (PLQY) of ∼95%, and a long decay lifetime of ∼357.7 μs (Figure c), almost identical to those of single crystals. These results suggest that the newly developed synthetic method is viable to produce high-quality organic metal halide hybrids on a large scale while avoiding the introduction of defects occurring in grounding single crystals or mechanochemical synthesis. , …”