Journal of the American Chemical Society, Vol.139, No.37, 12887-12890, 2017
Reversible Exchange of L-Type and Bound-Ion-Pair X-Type Ligation on Cadmium Selenide Quantum Belts
CdSe quantum belts of composition {CdSe[n-octylamine](0.53)} and protic acids HX (X = Cl, Br, NO3, acetate (OAc), and benzoate (OBz)) react to exchange the L-type amine ligation to bound-ion-pair X-type ligation. The latter ligation has X- anions bound to the nanocrystal surfaces and closely associated LH+ counter-cations (protonated n-octylamine or tri-n-octylphosphine (TOP) to balance the surface charges. The compositions of the exchanged QBs are {CdSe[Br](0.44)[n-octylammonium](0.41)}, {CdSe[NO3](0.10)[TOPH](0.12)}, {CdSe[OBz](0.08)[n-octylammonium](0.02)[TOPH](0.06)}, and {CdSe[OAc](0.16)[n-octylammonium](0.02)[TOPH](0.14)}. (The HCl-exchanged QBs are insufficiently stable for elemental analysis.) The bound-ion-pair X-type ligation is fully reversed to L-type n-octylamine ligation in the cases of X = NO3, acetate, and benzoate. The ligand exchanges are monitored by absorption spectroscopy, and the exchanged, bound-ion-pair X-type ligated nanocrystals are characterized by a range of methods.