Tuning from Quantum Dots to Magic Sized Clusters of CsPbBr3 Using Novel Planar Ligands Based on the Trivalent Nitrate Coordination Complex.

We report the first demonstration of using trivalent metal hydrated nitrate coordination complexes (TMHNCCs) as novel passivation ligands to control the synthesis of magic sized clusters (MSCs) and quantum dots (QDs) of CsPbBr3 perovskite at room temperature. We can easily tune from QDs to MSCs or produce a mixture of the two by changing the amount of TMHNCC ligands used, with more ligands favoring MSCs. The original TMHNCC introduced, aluminum nitrate nonahydrate [ANN, Al(NO3)3·9H2O], led to the production of aluminum dihydroxide nitrate tetrahydrate {ADNT, [Al(OH)2(NO3)]·4H2O}, with the assistance of oleic acid (OA) and oleylamine (OAm). Through several control experiments, we determined that ADNT is the primary ligand for effectively passivating the MSCs and QDs, with OAm being essential for deprotonating ANN and OA for adjusting the pH of the reaction system. We suggest that ADNT is planar on the surface of the MSCs or QDs with its NO3- and OH- groups binding to the Cs+ and Pb2+ defect sites and Al3+ binding to the Br- defect sites of the MSCs or QDs.