Postsynthetic Doping of MnCl2 Molecules into Preformed CsPbBr3 Perovskite Nanocrystals via a Halide Exchange‐Driven Cation Exchange

Unlike widely used postsynthetic halide exchange for CsPbX3 (X is halide) perovskite nanocrystals (NCs), cation exchange of Pb is of a great challenge due to the rigid nature of the Pb cationic sublattice. Actually, cation exchange has more potential for rendering NCs with peculiar properties. Herein, a novel halide exchange‐driven cation exchange (HEDCE) strategy is developed to prepare dually emitting Mn‐doped CsPb(Cl/Br)3 NCs via postsynthetic replacement of partial Pb in preformed perovskite NCs. The basic idea for HEDCE is that the partial cation exchange of Pb by Mn has a large probability to occur as a concomitant result for opening the rigid halide octahedron structure around Pb during halide exchange. Compared to traditional ionic exchange, HEDCE is featured by proceeding of halide exchange and cation exchange at the same time and lattice site. The time and space requirements make only MnCl2 molecules (rather than mixture of Mn and Cl ions) capable of doping into perovskite NCs. This special molecular doping nature results in a series of unusual phenomenon, including long reaction time, core–shell structured mid states with triple emission bands, and dopant molecules composition‐dependent doping process. As‐prepared dual‐emitting Mn‐doped CsPb(Cl/Br)3 NCs are available for ratiometric temperature sensing. A novel halide exchange‐driven cation exchange strategy is developed to prepare dually emitting Mn‐doped CsPb(Cl/Br)3 nanocrystals (NCs). The key is the simultaneous reactions of halide exchange and cation exchange at the same time and lattice site, which can be satisfied only by direct doping of MnCl2 molecules into NCs.