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Issue 9, 2015
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A blue luminescent MOF as a rapid turn-off/turn-on detector for H2O, O2 and CH2Cl2, MeCN: 3[Ce(Im)3ImH]·ImH

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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 Ce3+ – 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 Ce3+-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.

Graphical abstract: A blue luminescent MOF as a rapid turn-off/turn-on detector for H2O, O2 and CH2Cl2, MeCN: 3∞[Ce(Im)3ImH]·ImH

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Publication details

The article was received on 21 Nov 2014, accepted on 14 Jan 2015 and first published on 15 Jan 2015


Article type: Paper
DOI: 10.1039/C4DT03578J
Citation: Dalton Trans., 2015,44, 4070-4079
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    A blue luminescent MOF as a rapid turn-off/turn-on detector for H2O, O2 and CH2Cl2, MeCN: 3[Ce(Im)3ImH]·ImH

    L. V. Meyer, F. Schönfeld, A. Zurawski, M. Mai, C. Feldmann and K. Müller-Buschbaum, Dalton Trans., 2015, 44, 4070
    DOI: 10.1039/C4DT03578J

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