Reaction of n-octylamine-passivated {CdSe[n-octylamine](0.53±0.06)} quantum belts with anhydrous metal carboxylates M(oleate)2 (M = Cd, Zn) results in a rapid exchange of the L-type amine passivation for Z-type M(oleate)2 passivation. The cadmium-carboxylate derivative is determined to have the composition {CdSe[Cd(oleate)2](0.19±0.02)}. The morphologies and crystal structures of the quantum belts are largely unaffected by the exchange processes. Addition of n-octylamine or oleylamine to the M(oleate)2-passivated quantum belts removes M(oleate)2 and restores the L-type amine passivation. Analogous, reversible surface exchanges are also demonstrated for CdS quantum platelets. The absorption and emission spectra of the quantum belts and platelets are reversibly shifted to lower energy by M(oleate)2 passivation vs amine passivation. The largest shift of 140 meV is observed for the Cd(oleate)2-passivated CdSe quantum belts. These shifts are attributed entirely to changes in the strain states in the Zn(oleate)2-passivated nanocrystals, whereas changes in strain states and confinement dimensions contribute roughly equally to the shifts in the Cd(oleate)2-passivated nanocrystals. Addition of Cd(oleate)2, which electronically couples to the nanocrystal lattices, increases the effective thickness of the belts and platelets by approximately a half of a monolayer, thus increasing the confinement dimension.
Five
new, discretely sized, magic-size II–VI nanoclusters are synthesized
in primary-amine bilayer templates and are isolated as the derivatives
[(CdS)34(n-butylamine)18],
[(ZnS)34(n-butylamine)34],
[(ZnSe)13(n-butylamine)13],
[(CdTe)13(n-propylamine)13],
and [(ZnTe)13(n-butylamine)13]. The nanoclusters are characterized by elemental analysis, UV–visible
absorption spectroscopy, laser-desorption-ionization mass spectrometry,
and transmission electron microscopy. Four of the nanocluster precursors
are converted to wurtzitic CdS, ZnS, and ZnSe quantum platelets and
CdTe quantum belts, respectively, under mild conditions.
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