Long-afterglow metal-organic frameworks: reversible guest-induced phosphorescence tunability

Luminescent metal-organic frameworks (MOFs) have received much attention due to their wide structural tunability and potential application in light-emitting diodes, biological imaging and chemical sensors. However, successful examples of long-persistent afterglow MOFs are still quite limited to date. In this work, we report that two types of Zn-terephthalate (TPA) MOFs (namely [Zn(TPA)(DMF)] (1-DMF) and MOF-5) could exhibit an obvious room-temperature afterglow emission with a time-resolved luminescence lifetime as high as 0.47 seconds. The phosphorescence-based afterglow was also highly sensitive to the temperature, and the reversible emission intensity could be recycled under high/low temperatures. Moreover, both 1-DMF and MOF-5 showed highly tunable afterglow phosphorescence colors (from cyan to yellow and from green to red, respectively) upon treatment with pyridine solution. The fluorescence/phosphorescence emission color of MOF-5 can be reversibly switched due to the addition and removal of a pyridine guest to and from the host nanochannel, as shown in both experimental and computational studies. Therefore, this work not only shows a facile method to develop MOF-based long-afterglow materials at room temperature, but also presents a strategy to tune their phosphorescence in a wide range based on host-guest interactions.