Because of the involvement of the gas-solid diffusion, device fabrication, and the relatively complex photophysical process, the lanthanide complexes are rarely exploited as fluorescence sensors for volatile compound (VC) detection. Herein, we report the first example of a discrete 3D Ln-based architecture as a sensor for VCs. The designed Eu4L4 tetrahedral cage shows highly selective, rapidly reversible, and turn-on emissive responses toward volatile amines/NH3 in a spin-coated film. Through the comprehensive spectral characteristic and density functional theory calculation, an intermolecular weak nucleophilic interaction is proposed for this response mechanism. Combining this weak interactions with the permeability of the cage, the film presents subsecond to second timescales rapid response; combining the fitting electrophilic capability of the β-diketonate units to amine nitrogen with the tunable intramolecular charge-transfer feature, the cage shows excellent selectivity and turn-on emissive response. This work provides a new clue to develop the lanthanide complexes as luminescence probes for VCs.
Keywords: lanthanide cage; luminescence sensor; supramolecule; volatile amines; weak nucleophilic interaction.