Highly Luminescent Crystalline Sponge: Sensing Properties and Direct X-ray Visualization of the Substrates
Abstract
A phenomenon of crystalline sponge is represented by guest-dependent structural fluidity of the host polymeric lattice in highly crystalline sorbents, such as metal-organic frameworks, driven by multiple weak intermolecular interactions. Such induced fitting in MOFs is a valuable property in selective adsorption, guest determination by single-crystal XRD and in-situ structural analysis under external stimuli. In this work, a porous three-dimensional metal-organic framework [Eu2(DMF)4(ttdc)3]·4.45DMF (1DMF; DMF = N,N-dimethylformamide, ttdc2- = trans-thienothiophenedicarboxylate anion) was applied as a crystalline sponge bearing luminescent functionality to couple its sensing properties with direct structural determination of the adsorbed molecules. As a result, the paper discusses crystal structures and luminescent properties for the successfully obtained new adducts with the crystallographic formulae [Eu2(DMSO)4(ttdc)3]·2.5DMSO·2.2H2O (1DMSO; DMSO = dimethylsulfoxide), [Eu2(DMF)4(ttdc)3]·3phet (1phet; phet = phenylethanal) and [Eu2(DMF)3.5(cin)0.5(ttdc)3]·1.64cin (1cin; cin = trans-cinnamaldehyde). As a result of inclusion of DMSO into 1, a slight increase in the quantum yield and excited state phosphorescence lifetime was observed, while the adsorption of phet leads to a considerable (up to three times) decrease in the corresponding values. The incorporation of cinnamal results in a full quenching of QY, from 20% down to zero, and a more than order of magnitude diminishing…
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