Stimulus-Responsive Lanthanide MOF Materials Encapsulated with Viologen Derivatives: Characterization, Photophysical Properties and Sensing on Nitrophenols.

Abstract

Viologens (1,1'-disubstituted 4,4'-bipyridyls) possessing electron-deficient properties and redox activity are a class of suitable chromophores to assemble metal-organic hybrid photochromic materials. Thus, viologen-functionalized metal-organic frameworks (MOFs) have attracted much attention for their photochromic properties; however, the syntheses of lanthanide-viologen hybrid crystalline photochromic materials still face many challenges. For example, the structures and properties of the final products are difficult to predict and are limited by molecular configurations. In this work, host-guest composite-material Ln-NH2 BDC-pbpy MOFs were constructed by encapsulating viologen derivative pbpyCl2 . The pbpy2+ moieties are uniformly embed by their π-π conjugation in the pores of the 3D structure by electrostatic interactions. Due to the encapsulation of the chromophore pbpy2+ moieties, Ln-NH2 BDC-pbpy MOFs have reversible photochromic properties: they can change color after irradiation and can return to the original color after being protected from light or heating. Interestingly, the fluorescence intensity decreases with illumination time and recovers in the dark. As a result, Ln-NH2 BDC-pbpy MOFs show both photochromic and photomodulated fluorescence. Based on the outstanding fluorescence performance of the Ln-NH2 BDC-pbpy MOFs, they also show a wonderful effect for detecting nitrophenols, especially TNP.