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We demonstrate for the first time highly luminescent blue-emitting CdZnS/ZnS wurtzite core/shell nanorods (NRs) that show electric-field-induced fluorescence switching properties. Uniform CdZnS NRs were rapidly synthesized by injecting sulfur powder dissolved in 1-octadecene into a flask containing phosphonic acid ligands, and subsequently ZnS shells were coated using reagents consisting of sulfur powder, zinc sulfate heptahydrate, and oleylamine. The growth of high-quality ZnS shells resulted in a dramatically increased photoluminescence (PL) quantum yield (QY) of ∼40% with a minimal red-shift of the blue PL peak, which indicates that the combination of reagents successfully controlled a large number of defects appearing on the surface of the NR cores. By pre-annealing CdZnS cores before growing ZnS shells, we could achieve an additional increase in the maximum PL QY to 50%, decreases in both the full width at half maximum (FWHM) and the red-shift of the PL peak, and improved electric-field-induced fluorescence switching performance. Density functional theory calculations reveal that the effective relaxation of strain accumulating on the NR core during shell growth is the key to our successful synthesis of blue-emitting NRs, and that the additional improvement in performance obtained through the pre-annealing process results from the elimination of sulfur vacancies appearing at the surface of the NR core.

A series of mono-, di-, and tri-phosphine oxide substituted triarylboranes, Mes2BAr (1), MesBAr2 (2), and BAr3 (3) (Ar = 4-(Ph2PO)-2,6-Me2-C6H2) were prepared to investigate the effect of a phosphine oxide group (Ph2PO) on Lewis acidity enhancement of triarylboranes. The X-ray crystal structure of 3 revealed peripheral decoration of Ph2PO groups with a C3-axis perpendicular to the trigonal boron center. UV/Vis absorption and PL spectra indicated a significant contribution of π(Mes or phenylene) → pπ(B) charge transfer in the lower-energy electronic transition. The reduction potential measured by cyclic voltammetry showed apparent LUMO stabilization by introduction of phosphine oxide groups, the extent of which gradually increased with the increasing number of phosphine oxide groups. Lewis acidity enhancement was also supported by the gradual increase in fluoride ion affinity in the order 3 > 2 > 1. Theoretical calculations suggest that introduction of a Ph2PO group into a triarylborane significantly enhances the Lewis acidity of the boron center via an inductive electron-withdrawing effect and this effect is additive for multiple phosphine oxide groups.