With increasing global industrialization, it is urgent and challenging to develop multifunctional species for detection and adsorption in the environment. For this purpose, a novel anionic heterometallic organic framework, [(CH)NH][CaEu(CAM)(HO)]·4HO·4DMF (), is hydrothermally synthesized based on chelidamic acid (HCAM). Single crystal analysis shows that features two different oxygen-rich channels along the -axis in which one CAM bridges two sextuple-coordinated Ca and two octuple-coordinated Eu with a μ-η: η: η: η: η: η new chelating and bridging mode. The characteristic bright red emission and superior hydrostability of under harsh acidic and basic conditions benefit it by acting as a highly sensitive sensor for Fe and 3-nitrophenol (3-NP) with extremely low LODs through remarkable quenching. The combination of experiments and theoretical calculations for sensing mechanisms shows that the competitive absorption and interaction are responsible for Fe-induced selective emission quenching, while that for 3-NP is the result of the synergism of host-guest chemistry and the inner filter effect. Meanwhile, the assimilation of negative charge plus channels renders a highly selective adsorbent for methylene blue (MB) due to a synergy of electrostatic affinity, ion-dipole interaction, and size matching. Of note is the reusability of toward Fe/3-NP sensing and MB adsorption besides its fast response. These findings could be very useful in guiding the development of multifunctional Ln-MOFs for sensing and adsorption applications in water media.
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http://dx.doi.org/10.1021/acs.inorgchem.4c00320 | DOI Listing |
Inorg Chem
January 2025
College of Chemistry and Chemical Engineering, Xi'an Shiyou University, Xi'an 710065, China.
Luminescent lanthanide compounds stand out for their distinctive characteristics including narrow emission bands, substantial Stokes shifts, high quantum yields, and unique luminescent colors. However, Ln is highly susceptible to vibrational quenching from X-H (X = O/N) high-energy oscillators in the embedded organic antenna, resulting in significant nonradiative energy dissipation of the D excited states of Ln. Herein, we introduce a strategy based on supramolecular interactions to modulate the nonradiative transitions in a new Zn-Tb heterometallic compound, [ZnTb(HL)(NO)Cl]·2CHCN·HO (), based on a phenyl-substituted pyrazolinone-modified salicylamide-imide ligand ().
View Article and Find Full Text PDFDalton Trans
January 2025
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, P. R. China.
In the history of magnetochemistry development, lanthanide-transition (3d-4f) heterometallic compounds have been considered an attractive candidate for magnetic refrigerants. Herein, a series of heterometallic compounds have been designed and templated by CO anions, that is, {[LnNi(L)(CO)(HO)]·HO} [Ln = Gd (. Gd2Ni) = Sm (.
View Article and Find Full Text PDFInorg Chem
January 2025
MOE Key Laboratory of Cluster Science, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, China.
A novel antimonotungstate (AT)-based heterometallic framework {[Er(HO)][Fe(Hpdc)(B-β-SbWO)]}·50HO (, Hpdc = pyridine-2,5-dicarboxylic acid) was obtained through a synergistic strategy of in situ-generated transition-metal-encapsulated polyoxometalate (POM) building units and the substitution reaction. Its structural unit is composed of a tetra-Fe-substituted Krebs-type [Fe(Hpdc)(B-β-SbWO)] subunit and two [Er(HO)] cations. This subunit can be regarded as a product of carboxylic oxygen atoms of Hpdc ligands replacing active water ligands in the [Fe(HO)(B-β-SbWO)] species.
View Article and Find Full Text PDFMolecules
December 2024
CP2M-ESCPE Lyon, CNRS, University Claude Bernard Lyon 1, UMR 5128, 43 Bd du 11 Nov. 1918, CEDEX, 69616 Villeurbanne, France.
TiO:Eu nanoparticles with varying europium concentrations were successfully synthesized via a one-pot sol-gel approach using a molecular heterometallic single-source precursor (SSP) Eu-Ti. For comparison, nanomaterials with similar europium levels were also produced by impregnating europium salts onto the same TiO substrate. All the nanomaterials were thoroughly characterized using Eu elemental analysis, powder X-ray diffraction (XRD), scanning (SEM), transmission (TEM), scanning transmission electron microscopy (STEM), Brunauer-Emmett-Teller (BET) analysis, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and photoluminescence (PL).
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, National & Local United Engineering Laboratory for Power Battery Institution, Northeast Normal University, Changchun, Jilin, 130024, China.
Construction of metal-organic cages (MOCs) with internal modifications is a promising avenue to build enzyme-like cavities and unlocking the mystery of highly catalytic activity and selectivity of enzymes. However, current interests are mainly focused on single-metal-node cages, little achievement has been expended to metallocluster-based architectures, and the in situ endogenous generation of metal clusters. Herein, based on the hard-soft-acids-bases (HSAB), the metallocluster-based heterometallic MOC (CuVMOP) constructed of [CuOPz] and [VO(OCH)(SO)(CO)] clusters was obtained by one-pot method.
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