Highly‐Doped Lanthanide‐Based Nanocrystals with Cooperative Core‐Shell Upconversion Emission for Multicomponent One‐Pot Chemical Transformations

Abstract

In order to apply near infrared (NIR) light‐activated upconversion nanocrystals (UCNCs) in photochemistry, extremely bright luminescence is needed to excite the ultraviolet (UV)‐visible light absorbing photocatalyst/substrate. In this study, a multilayered UCNC consisting of a β‐NaYF4:Yb0.2, Tm0.005 core, heavily Yb3+‐doped β‐NaYbF4:Y0.09, Tm0.01 intermediate shell, and inert β‐NaYF4 outer shell is prepared. By compartmentalizing the sensitizer (Yb3+)‐activator (Tm3+) pair in the core and intermediate shell with different concentration ratios, a cooperative luminescence effect is discovered. Apart from core emission, energy harvesting followed by sequential energy transfer from a high density of neighboring Yb3+ to Tm3+ in the intermediate shell induces a large population of excited emitter ions. Furthermore, after back energy transfer from the core to intermediate shell, the energy is not quenched by intrinsic trap sites but is instead transferred to Tm3+, further boosting emission in the UV, blue, and NIR regions. The exceptionally bright UCNC is then used to drive NIR‐light‐activated one‐pot multicomponent reactions involving the upconversion energy transfer from UCNC to UV‐visible light absorbing photocatalyst/substrate, Lewis acid catalytic activity of the lanthanide ions (Y3+) on the surface, and photothermal property of the UCNC. The reactions studied include the deacetalization‐Knoevenagel condensation reaction, photooxidation‐cyanation reaction, and hydrodehalogenation‐cyanosilylation reaction.