Redox Metal-Organic Framework for Photocatalytic Organic Transformation: The Role of Tetrazine Function in Radical-Anion Pathway.

Linker functionalization is a practical strategy to extend the applications of metal-organic frameworks (MOFs) in various fields. Here, this strategy is applied to synthesize a tetrazine-functionalized MOF [TMU-34(-2H), formulated [Zn(OBA) (DPT)]·DMF; HOBA and DPT are 4,4'-oxybis(benzoic acid) and 3,6-di(pyridin-4-yl)-1,2,4,5-tetrazine] for efficient photocatalytic synthesis of disulfides and benzimidazoles with maximum conversion after 90 and 120 min, respectively. The photocatalytic activity of TMU-34(-2H) originates from the electronic properties of tetrazine function, including absorption in the visible region and photogenerated redox activity.

A Dihydrotetrazine-Functionalized Metal-Organic Framework as a Highly Selective Luminescent Host-Guest Sensor for Detection of 2,4,6-Trinitrophenol.

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)(HDPT)]·DMF, where HOBA is 4,4'-oxybis(benzoic acid) and HDPT 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 M, = 182663 mol L), in the presence of other substituted NACs especially -NH-substituted NACs.