Unraveling the mechanochemical synthesis and luminescence in Mn-II-based two-dimensional hybrid perovskite (C4H9NH3)(2)PbCl4

The mechanochemical route is a facile and fast way and has received much attention for developing versatile advanced functional materials. Herein, we reported a mechanochemical synthesis for incorporating divalent manganese ions (Mn^II) into a two-dimensional (2D) hybrid perovskite (C₄H₉NH₃)₂PbCl₄. The mild external stimuli originating from the grinding at room temperature enabled the formation of MnII-doped 2D hybrid perovskites, and rapidly changed the luminescence characteristics. The photoluminescence analyses show that the violet and orange emissions are attributed to (C₄H₉NH₃)₂Pb_1–xMn_xCl₄ band-edge emission and the T₁→⁶A₁ transition of Mn²⁺ resulting from an efficient energy transfer process, respectively. Site preference and distribution of the doped Mn²⁺ cations on the locations of Pb²⁺ were analyzed. The formation energy calculated by the density functional theory (DFT) indicates that the Mn²⁺ ions can rapidly enter the crystal lattice due to the unique 2D crystal structure of the hybrid perovskite. Such a case of mechanochemical synthesis for the 2D hybrid perovskite motivates many novel emerging materials and the related applications.