A multifunctional Eu-MOF with multi-color and proton conduction switching and its anti-counterfeiting applications

Abstract

Lanthanide metal-organic frameworks (Ln-MOFs) have exhibited remarkable capabilities in color change, luminescence, proton conduction through the strategic modification of metal nodes, organic ligands and channels or pores. By modifying the electron-deficient bipyridinium to contain carboxylic acid moieties and coordinating them with the luninescent Eu3+ ion, a unique and versatile Eu-MOF has been synthesized. Under UV light conditions, the complex shows an obvious color change from colorless to blue, which is due to the formation of viologen radicals after photoinduced electron transfer (PIET) process. As we all know, the changed color is caused by the alteration of absorption intensity, ultimately impacting its luminescence as well. Thus, the bright and strong red fluorescence of this complex is quenched upon continuous UV light irradiation, which may be attributed to intramolecular energy transfer from the excited state of the europium ion to the colored state of the CV ligand. Based on the control of multiple colors of the complex, the designed encryption model can realize multiple anti-counterfeiting of real numbers. In addition, the conductivity of this compound increases significantly after UV illumination, showing excellent photo-modulated proton conductivity. In short, our work has proposed a multifunctional bipyridinium-based Ln-MOF with photochromism, photo-switchable photoluminescence and proton conduction, which offers valuable insights for the creation of versatile switchable materials based on MOFs.