title: A blue luminescent MOF as a rapid turn-off/turn-on detector for H2O, O2 and CH2Cl2, MeCN: ∞³[Ce(Im)3ImH]·ImH.
abstract: The blue emitting luminescent MOF ∞³[Ce(Im)3ImH]·ImH forms a 3D-framework with Kagomé net topology. The framework exhibits an intense blue luminescence which can be retained upon activation of the MOF with the formula ∞³[Ce(Im)3ImH]. The luminescence is metal-based due to parity-allowed 5d-4f-transitions. Time-dependent investigations of the interaction with liquid and gas analytes show that the MOF – by utilising 5d-4f-transitions of Ce(3+) – can be used as a high-speed "turn-off" detector for water and oxygen in dry air. Other protic or polar solvents, like methanol, acetone or pyridine, which also show a "turn-off"-effect can be distinguished from water-detection either on a time scale (ranging up to 250,000 : 1) or a shift of the chromaticity, the latter being pronounced for MeOH. The fast time-dependent decrease of the luminescence intensity for water arises from an extremely fast hydrolysis and is irreversible. Polar aprotic molecules like dichloromethane and acetonitrile can also result in a "turn-on"-effect of the luminescence intensity due to their behaviour as additional sensitizers for Ce(3+)-emission. We conclude that the cerium-MOF can be utilised in gas and liquid sensing applications as a detector material for water and oxygen in dry air. The luminescence is intense with good quantum yield between 55% (as-synthesised) and 36% (activated). This implies that only milligram amounts of the material are needed to detect the analyte species and is especially useful, as the MOF can be directly used as-synthesised for water detection in applications for which an irreversible signal change is desired, e.g. preventing a signal change upon unwanted re-drying.
authors.affiliation: Institute of Inorganic Chemistry, Julius-Maximilians-University Würzburg, Am Hubland, 97074 Würzburg, Germany. k.mueller-buschbaum@uni-wuerzburg.de.
authors.forename: L V
authors.initials: LV
authors.lastname: Meyer
authors.forename: F
authors.initials: F
authors.lastname: Schönfeld
authors.forename: A
authors.initials: A
authors.lastname: Zurawski
authors.forename: M
authors.initials: M
authors.lastname: Mai
authors.forename: C
authors.initials: C
authors.lastname: Feldmann
authors.forename: K
authors.initials: K
authors.lastname: Müller-Buschbaum