A novel luminescent microporous lanthanide metal-organic framework (Ln-MOF) based on a urea-containing ligand has been successfully assembled. Structural analysis revealed that the framework features two types of 1D channels, with urea N-H bonds projecting into the pores. Luminescence studies have revealed that the Ln-MOF exhibits high sensitivity, good selectivity, and a fast luminescence quenching response towards Fe , Cr anions, and picric acid. In particular, in the detection of Cr O and picric acid, the Ln-MOF can be simply and quickly regenerated, thus exhibiting excellent recyclability. To the best of our knowledge, this is the first example of a multi-responsive luminescent Ln-MOF sensor for Fe , Cr anions, and picric acid based on a urea derivative. This Ln-MOF may potentially be used as a multi-responsive regenerable luminescent sensor for the quantitative detection of toxic and harmful substances.
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.
A novel "turn-on" phosphorescent chemodosimeter based on a cyclometalated Ir(III) complex has been designed and synthesized, which displays high selectivity and sensitivity toward Hg(2+) in aqueous media with a broad pH range of 4-10. Furthermore, by time-resolved photoluminescence techniques, some interferences from the short-lived background fluorescence can be eliminated effectively and the signal-to-noise ratio of the emission detection can be improved distinctly by using the chemodosimeter. Finally, the chemodosimeter can be used to monitor Hg(2+) effectively in living cells by confocal luminescence imaging.
A series of unique homochiral lanthanide tetranuclear quadruple-stranded helicates have been self-assembled controllably by using the intrinsic advantages of chiral bridging ligands, (S)-H L and (R)-H L, and lanthanide ions with high coordination numbers. The self-assembly process of these chiral helicates not only ensures the structural stability and quadruple-stranded feature of lanthanide cluster in the solid state and solution, but also achieves effective transfer and amplification of the chirality code from the ligand to a higher supramolecular level. Moreover, through using optical rotation, circular dichroism spectra analysis, and luminescence measurements, we demonstrate that these chiral lanthanide helicates could serve as sensitive and multi-responsive sensors to recognize and detect F anions based on the change of chiral signal and NIR luminescence simultaneously, which represents a meaningful exploration for developing functional lanthanide-based polynuclear clusters.
Two series of anion-induced 3d-4f luminescent clusters ZnII2LnIII2L4 (LnIII = Eu3+, Tb3+, Er3+, Yb3+, Nd3+) and ZnII4LnIII2L4 (LnIII = Tb3+, Nd3+) based on μ3-OH group were synthesized and characterized. The difference in anions not only leads to significant structural changes, but also changes the luminescent properties of the 3d-4f coordination clusters. These complexes show excellent catalytic performance for CO2 conversion to obtain cyclic carbonates with wide substrate scopes and high selectivity under mild conditions. Turnover numbers were up to 9000, and turnover frequencies obtained were 660 h-1. The ligand is simple and the complexes are easily obtained even on a large scale. Moreover, these complexes also feature lanthanide-characterized luminescence both in visible and near infrared regions with relatively long luminescence lifetimes and high quantum yields, suggesting promising multifunctional applications.
A series of 4-nuclear lanthanide clusters supported by organic ligands Zn3LnL4 (Ln = Dy(1), Gd(2), Er(3)) were synthesized. These helicates could be used to convert CO2 into cyclic carbonates with TOF up to 38 000 h−1, without being influenced by moisture or air.
Cobalt-based nanomaterials are promising candidates as efficient, affordable, and sustainable alternative electrocatalysts for the oxygen evolution reaction (OER). However, the catalytic efficiency of traditional nanomaterials is still far below what is expected, because of their low stability in basic solutions and poor active site exposure yield. Here a unique hybrid nanomaterial comprising Co@Co3O4 core-shell nanoparticle (NP) encapsulated N-doped mesoporous carbon cages on reduced graphene oxide (denoted as Co@Co3O4@NMCC/rGO) is successfully synthesized via a carbonization and subsequent oxidation strategy of a graphene oxide (GO)-based metal-organic framework (MOF). Impressively, the special carbon cage structure is very important for not only leading to a large active surface area, enhanced mass/charge transport capability, and easy release of gas bubbles, but also preventing Co@Co3O4 NPs from aggregation and peeling off during prolonged electrochemical reactions. As a result, in alkaline media, the resulting hybrid materials catalyze the OER with a low onset potential of ∼1.50 V (vs. RHE) and an over-potential of only 340 mV to achieve a stable current density of 10 mA cm(-2) for at least 25 h. In addition, metallic Co cores in Co@Co3O4 provide an alternative way for electron transport and accelerate the OER rate.
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