Recent progress has been made on the synthesis and characterization of metal halide perovskite magic-sized clusters (PMSCs) with ABX ₃ composition (A = CH₃NH₃ ⁺ or Cs⁺, B = Pb²⁺, and X = Cl^-, Br^-, or I^-). However, their mechanism of growth and structure is still not well understood. In our effort to understand their structure and growth, we discovered that a new species can be formed without the CH₃NH₃ ⁺ component, which we name as molecular clusters (MCs). Specifically, CH₃NH₃PbBr₃ PMSCs, with a characteristic absorption peak at 424 nm, are synthesized using PbBr₂ and CH₃NH₃Br as precursors and butylamine (BTYA) and valeric acid (VA) as ligands, while MCs, with an absorption peak at 402 nm, are synthesized using solely PbBr₂ and BTYA, without CH₃NH₃Br. Interestingly, PMSCs are converted spontaneously overtime into MCs. An isosbestic point in their electronic absorption spectra indicates a direct interplay between the PMSCs and MCs. Therefore, we suggest that the MCs are precursors to the PMSCs. From spectroscopic and extended X-ray absorption fine structure (EXAFS) results, we propose some tentative structural models for the MCs. The discovery of the MCs is critical to understanding the growth of PMSCs as well as larger perovskite quantum dots (PQDs) or nanocrystals (PNCs).

Mn-doped CsPbBr₃ perovskite magic sized clusters (PMSCs) are synthesized for the first time using benzoic acid and benzylamine as passivating ligands and MnCl₂·4H₂O and MnBr₂ as the Mn²⁺ dopant sources at room temperature. The same approach is used to prepare Mn-doped CsPbBr₃ perovskite quantum dots (PQDs). The concentration of MnX₂ (X = Cl or Br) affects the excitonic absorption of the PMSCs and PQDs. A higher concentration of MnX₂ favors PMSCs over PQDs as well as higher photoluminescence (PL) quantum yields (QYs) and PL stability. The large ratio between the characteristic Mn emission (∼590 nm) and the host band-edge emission shows efficient energy transfer from the host exciton to the Mn²⁺ dopant. PL excitation, electron paramagnetic resonance, and time-resolved PL results all support Mn²⁺ doping in CsPbBr₃, which likely replaces Pb²⁺ ions. This study establishes a new method for synthesizing Mn-doped PMSCs with good PL stability, high PLQY and highly effective passivation.