Regular patterns of the effects of hydrogen-containing additives on the formation of CdSe monomer

It is unclear at the molecular level why HY (HY = RSH, or ROH, or RNH2) with HPPh2 additives kinetically affects the reaction pathway to the formation of different monomers (Ph2P-SeCd-Y or Ph2P-SeCdSe-Y) in the systhesis of semiconductor nanocrystals. In the present work, it was found that in a [Cd(OA)2 + Se[double bond, length as m-dash]P(C8H17)3 + HPPh2 + HY] mixture, HY behaves as a mediator for the formation of the initial kind of monomer, besides as a hydrogen/proton donor in the release of oleic acid and as an accelerant in the Se-P bond cleavage, which follows the mechanism of hydrogen-shift/nucleophilic-attack. The capability of the HY additive to provide a H-source decreases in the order SePPh2H > RSH > HPPh2 > ROH > RNH2, while the performance of HY to accelerate Se-P bond cleavage decreases in the order HPPh2 > RSH > RNH2 > ROH. The capacity of HY to promote the formation of the Ph2P-SeCd-Y monomer decreases in the order RSH > HPPh2 > ROH > RNH2, while the effect of HY to drive the formation of the Ph2P-SeCdSe-Y monomer decreases in the order HPPh2 > RSH > RNH2 > ROH. The activation strain energy plays a key role in both the Se-P and H-Y bond cleavage, which correlates negatively to the size of the coordinated atom radius. When only HPPh2 is present without other HY species (HY = RNH2, or RSH, or ROH), Ph2P-SeCdSe-PPh2 is preferentially formed. Alternatively, when both HY (HY = RNH2, or RSH, or ROH) and HPPh2 are present, Ph2P-SeCd-Y is favorably formed. For the formation of Ph2P-SeCd-Y (Y = -PPh2, -SR, -OR, and -NHR), SePPh2H embodies the catalytic performance, while HPPh2 serves as the catalyst for the formation of Ph2P-SeCdSe-Y (Y = -NHR or -OR). Our study brings a molecular-level insight into the relationship between the CdSe monomer and the phosphorous-containing side-product, which may advance the rational design and synthesis of quantum dots.