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

Abstract

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)(H 2 DPT) 0.5 ] n •DMF, where H 2 OBA is 4,4′-oxybis-(benzoic acid) and H 2 DPT 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 −NH 2 -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 −NH 2 -substituted NACs as the serious interferers.

Two Stable Cd-MOFs as Dual-Functional Materials with Luminescent Sensing of Antibiotics and Proton Conduction

“…Compared with the free H 4 L and H 2 biim ligands, 1 exhibits a significant red-shifted emission at 443 nm (λ ex = 292 nm) and 2 shows a slightly red-shifted emission around 423 nm upon irradiation at 283 nm (Figure S6b and S6c). The results show that the fluorescence of 1 and 2 is mainly attributed to the ligand-to-ligand charge transfer (LLCT). , At present, the research of MOF luminescent sensing mainly employs the solution system as the medium, combined with the excellent water stability and solid-state fluorescent characteristics of 1 and 2 ; thus, the fluorescent spectra of H 4 L, 1 , and 2 in aqueous solution were further tested. It can be observed that they show intense emission at λ em = 348 nm (λ ex = 300 nm) for H 4 L, λ em = 350 nm (λ ex = 295 nm) for 1 , and λ em = 332 nm (λ ex = 290 nm) for 2 in aqueous suspension (Figure ).…”

Explosive and pollutant nitroaromatic sensing through a Cd(II) based ladder shaped 1D coordination polymer

“…Luminescent properties of this kind of coordination polymers can be effectively utilized to sense different materials through the process of fluorescence quenching. Several coordination polymers based on d 10 metal systems were reported to effectively sense various nitroaromatic compounds through fluorescence quenching mechanism [ [65] , [66] , [67] , [68] , [69] , [70] , [71] , [72] , [73] , [74] ].…”

Fluorescent water‐stable Zn (II) coordination polymers for selective aqueous detection of nitrophenols

“…[20] Compared with the aforementioned fluorescent probes, coordination polymers (CPs) as fluorescent probes have recently received extensive attention by virtue of their high chemical stability, diverse structural topologies, and adjustable fluorescence emission. [21][22][23][24][25][26][27][28][29] Furthermore, regarding the precise structural information obtained for most CP sensors, it is possible to evaluate and optimize their structure-performance relationship at the atomic level.…”