Construction of Multifunctional Luminescent Lanthanide MOFs by Hydrogen Bond Functionalization for Picric Acid Detection and Fluorescent Dyes Encapsulation

Abstract

From the perspective of efficient and economical utilization of materials, it is very meaningful to achieve multifunctional performance in its assembly process, and this is also the future development trend of metal–organic framework (MOF) materials. As an important type of intermolecular interaction, hydrogen bonding is widely used in supramolecular self-assembly, molecular recognition, and catalytic organic reactions. Following the hydrogen bond functionalization construction strategy, we introduced urea–hydrogen bonding sites into the ligands and then introduced functionalized ligands into the MOF frameworks, which efficiently realized the construction of multifunctional lanthanide MOFs. Structural analysis indicated that the MOF consists of 2D layers with parallelogram holes and stacking into 3D frameworks through the N–H···O hydrogen bonding interactions. Interestingly, a functionalization ligand in the MOF frameworks plays three different roles: support, recognition, and both support and recognition. Thanks to the pores rich in urea sites and the excellent luminescent properties of lanthanide ions, the MOF can be used as a regenerable luminescent sensor for the efficient detection of picric acid. Moreover, two fluorescent dyes, such as perylene and fluorescein, can be encapsulated into the functionalized pores and show excellent dual-emitting performance, which proved that we have successfully adjusted the luminescent properties of Ln-MOF by introducing guest luminescent molecules. More importantly, the hydrogen bond functionalization construction strategy will provide some experimental reference for the construction of multifunctional MOF materials.

Lanthanide-based metal–organic framework materials as bifunctional fluorescence sensors toward acetylacetone and aspartic acid

“…16,17 Therefore, the reaction of lanthanide ions with suitable ligands has become an effective way to construct multifunctional lanthanide-based MOFs (Ln-MOFs). 18,19 In particular, the photoluminescence characteristics of Ln-MOFs expand the application in molecular switches and chemical sensors. [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] Many Ln-MOFs have been applied to detect metal cations, inorganic anions and small organic molecules.…”

“…18,19 In particular, the photoluminescence characteristics of Ln-MOFs expand the application in molecular switches and chemical sensors. [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] Many Ln-MOFs have been applied to detect metal cations, inorganic anions and small organic molecules. 25,26 However, there are few reports of Ln-MOFs for the detection of amino acids.…”

Noncovalent Interactions at Lanthanide Complexes

“…The combination of hydrogen bond donor or acceptor sites with a RAHB synthon into metal‐organic frameworks (MOFs) can have an additional advantage on their application in adsorption/separation, [109] catalysis, [110] molecular recognition, [111] etc. For example, the role of hydrogen bonding in lanthanide MOFs for the luminescence response, [112] picric acid detection and fluorescent dyes encapsulation, [113] etc. has already been demonstrated.…”

Epoxy Functional Composites Based on Lanthanide Metal–Organic Frameworks for Luminescent Polymer Materials

“…However, the preparation of this material requires a rather high temperature and pressure conditions. Among a diversity of metal–organic frameworks, lanthanide MOFs represent an important class of functional materials, largely due to their intrinsic luminescent properties such as long lifetimes, large Stokes shifts, and sharp emissions. , Therefore, it is attractive to explore new methods for the synthesis of Ln-MOF@polymer materials with remarkable luminescent properties. To date, hybrid MOF@polymer materials fabricated by postsynthetic polymerization revealed good stability and integrity (no release of MOF particles from a polymer matrix).…”