Cooperative performance of mixed-valent Eu(2+) /Eu(3+) in single-compound phosphors offers significant advantages in color rendering and luminescence efficiency, but their synthesis is challenging because of Eu(2+) oxidation. Using the tunable nature of the metal-ion nodes in metal-organic frameworks (MOFs), we present an in situ reduction and crystallization route for preparing MOFs and doping Eu(2+) /Eu(3+) with a controlled ratio. These materials exhibit rich photoluminescence, including intrinsic- and sensitized-emissions of Eu(2+) and Eu(3+) , and long-lived luminescence from charge transfer. Color rendering can be easily achieved by fine-tuning the valence states of Eu. A linear relation between temperature and the intensity ratio of Eu(2+) /Eu(3+) emissions provides outstanding properties for applications as self-calibrated luminescent thermometers with a wide working temperature range. Further incorporation of Tb(3+) into the MOFs results in white light, utilizing all Eu(2+) ,Tb(3+) , and Eu(3+) emissions in a single crystalline lattice.
Keywords: europium; luminescence; metal-organic frameworks; mixed valence; photoluminescence.
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