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. (Ph 4 P) 2 SbCl 5 and (Ph 4 P) 2 MnCl 4 were synthesized by grinding appropriate ratios of organic halide salt Ph 4 PCl with inorganic metal halide salts SbCl 3 and MnCl 2 , respectively. The structural and photophysical properties of mechanochemically synthesized (Ph 4 P) 2 SbCl 5 and (Ph 4 P) 2 MnCl 4 were characterized, which are almost identical to those of single crystals prepared by slow solution growth. By reacting Ph 4 PCl with both SbCl 3 and MnCl 2 , 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.