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

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 the...

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Bibliographic Details
Published in:Chemistry : a European journal 2023-01, Vol.29 (4), p.e202202810-n/a
Main Authors: Li, Hui‐Shu, Xing, Shang‐Hua, Xiao, Yao, Wang, Chen, Guan, Qing‐Lin, Bai, Feng‐Ying, Xing, Yong‐Heng, Xu, Fen
Format: Article
Language:English
Subjects:
aminoterephthalic acid
Chemistry
Chromophores
Composite materials
Conjugation
Electrostatic properties
Encapsulation
Fluorescence
fluorescent sensing
Irradiation
lanthanide MOFs
Luminous intensity
Metal-organic frameworks
Photochromism
photophysical properties
Radiation
viologen derivatives
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Summary: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‐NH2BDC‐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‐NH2BDC‐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‐NH2BDC‐pbpy MOFs show both photochromic and photomodulated fluorescence. Based on the outstanding fluorescence performance of the Ln‐NH2BDC‐pbpy MOFs, they also show a wonderful effect for detecting nitrophenols, especially TNP. Six novel 3D Ln‐NH2BDC MOFs encapsulating pbpyCl2 have been designed and synthesized. They are sensitive to visible light and exhibit a good reversible photochromic and photomodulated fluorescence phenomena. Moreover, they have a good detection effect on nitrophenols, especially 2,4,6‐trinitrophenol (TNP).
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202202810