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Luminescent metal-organic frameworks (LMOFs), as one branch of MOFs, have attracted considerable attention in recent years due to their good crystallinity, structural diversity, tunable porosity and easily induced fluorescence emission. Importantly, their photoluminescence (PL) properties can be adjusted by altering metal ions or metal clusters and organic ligands in one hybrid system. Among the various sensing applications, using LMOFs as chemical sensors to detect the explosive and environment pollution causing nitroaromatic compounds (NACs) is an important topic. In this account, we describe the recent advancements in the field of NAC detection by LMOFs based on the triphenylamine (TPA) unit as the π-conjugated fluorophore.

The combination of π-conjugated fluorophores within a hybrid system gives rise to a triphenylamine-functionalized material [Zn(bpba)(NO3)] (1) (Hbpba = 4-(bis(4-(pyridin-4-yl)phenyl)amino)benzoic acid). Compound 1 features a 2D + 2D → 2D parallel polycatenation structure with 63-hcb net. Photophysical studies revealed that the title phase showed superior sensitivity towards p-nitroaniline (p-NA) with a low detection limit (down to ∼0.10 ppm). Specifically, following a new detection route, vapor-sensing experiments using a saturated ethanol solution of nitroaromatic isomers have been established for the first time. Highly sensitive and selective detection of p-NA by the proposed material with a rapid response time (t = 30 s, QE > 90.0%) as compared to that via the control isomers (t = 60s, QE < 6.0%) demonstrates an attractive feasible route and a promising luminescent sensor for nitroaromatic detection.