Unveiling the Uncommon Fluorescent Recognition Mechanism towards Pertechnetate Using a Cationic Metal-Organic...

As one of most problematic radionuclides, technetium-99, mainly in the form of anionic pertechnetate (TcO₄ ^- ), exhibits high environmental mobility, long half-life, and radioactive hazard. Due to low charge density and high hydrophobicity for this tetrahedral anion, it is extremely difficult to recognize it in water. Seeking efficient and selective recognition method for TcO₄ ^- is still a big challenge. Herein, a new water-stable cationic metal-organic framework (ZJU-X8) was reported, bearing tetraphenylethylene pyrimidine-based aggregation-induced emission (AIE) ligands and attainable silver sites for TcO₄ ^- detection. ZJU-X8 underwent an obvious spectroscopic change from brilliant blue to flavovirens and exhibited splendid selectivity towards TcO₄ ^- . This uncommon fluorescent recognition mechanism was well elucidated by batch sorption experiments and DFT calculations. It was found that only TcO₄ ^- could enter into the body of ZJU-X8 through anion exchange whereas other competing anions were excluded outside. Subsequently, after interaction between TcO₄ ^- and silver ions, the electron polarizations from pyrimidine rings to Ag⁺ cations significantly lowered the energy level of the π* orbital and thus reduced the π-π* energy gap, resulting in a red-shift in the fluorescent spectra.