Reversible Z‑Type to L‑Type Ligand Exchangeon Zinc-Blende Cadmium Selenide Nanoplatelets

2020 
Three-monolayer CdSe nanoplatelets having the composition (CdSe)3[Cd­(OAc)0.77(oleate)1.23]0.78, large lateral dimensions, minimal strain distortions, and the zinc-blende crystal structure undergo Z-type to L-type ligand exchange with ethylenediamine, affording NPLs of composition (CdSe)3[en]0.67 (en = ethylenediamine). The L-type ligation of the (CdSe)3[en]0.67 (en = ethylenediamine) NPLs is exchanged for Z-type ligation with Cd­(oleate)2, Cd­(OAc)2, CdCl2, Zn­(oleate)2, and ZnCl2, giving NPLs having near to the ideal compositions of (CdSe)3[MX2]. All of the Z-type to L-type and L-type to Z-type ligand exchanges are kinetically slow, requiring several hours to reach completion, suggesting that a considerable surface reconstruction is required. In contrast, three-monolayer NPLs having a significant rolling distortion and four- and five-monolayer NPLs having small lateral dimensions are unstable to ethylenediamine, and Z-type to L-type ligand exchange is not achieved.
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