A Dihydrotetrazine-Functionalized Metal-Organic Framework as a Highly Selective Luminescent Host-Guest Sensor for...

Pore decoration of metal-organic frameworks (MOFs) with functional groups is a useful strategy to attain high selectivity toward specific analytes, especially in the presence of interfering molecules with similar structures and energy levels, through selective host-guest interactions. In this work, we applied a dihydrotetrazine-decorated MOF, TMU-34, with the formula [Zn(OBA)(H₂DPT)_0.5]·DMF, where H₂OBA is 4,4'-oxybis(benzoic acid) and H₂DPT is 3,6-bis(pyridin-4-yl)-1,4-dihydro-1,2,4,5-tetrazine, for the highly selective detection of phenolic NACs, especially TNP (94% quenching efficiency, detection limit 8.1 × 10^-6 M, K_SV = 182663 mol L^-1), in the presence of other substituted NACs especially -NH₂-substituted NACs. Investigations reveal that the quenching mechanism is dominated by photoinduced MOF-to-TNP electron transfer through possible hydrogen-bonding interactions between the phenolic hydroxyl group of TNP and dihydrotetrazine functions of TMU-34. Despite extensive publications on the detection of TNP in the presence of other NACs, the significance of this work will be elucidated if attention is paid to the fact that TMU-34 is among the rare and highly selective MOF-based TNP sensors in the presence of -NH₂-substituted NACs as the serious interferers.