Probing molecule-like isolated octahedra via phase stabilization of zero-dimensional cesium lead halide nanocrystals

Zero-dimensional (0D) inorganic perovskites have recently emerged as an interesting class of material owing to their intrinsic Pb(2+) emission, polaron formation, and large exciton binding energy. They have a unique quantum-confined structure, originating from the complete isolation of octahedra exhibiting single-molecule behavior. Herein, we probe the optical behavior of single-molecule-like isolated octahedra in 0D Cesium lead halide (Cs(4)PbX(6), X = Cl, Br/Cl, Br) nanocrystals through isovalent manganese doping at lead sites. The incorporation of manganese induced phase stabilization of 0D Cs(4)PbX(6) over CsPbX(3) by lowering the symmetry of PbX(6) via enhanced octahedral distortion. This approach enables the synthesis of CsPbX(3) free Cs(4)PbX(6) nanocrystals. A high photoluminescence quantum yield for manganese emission was obtained in colloidal (29%) and solid (21%, powder) forms. These performances can be attributed to structure-induced confinement effects, which enhance the energy transfer from localized host exciton states to Mn(2+) dopant within the isolated octahedra.