[reaction: see text] The synthesis of the novel Eu(III) cyclen complex, Eu1, is described. In buffered pH 7.4 water, the Eu(III) emission was "switched on" upon excitation of the Terpy antenna. In the presence of various transition-metal ions (e.g., Fe(II) and Ni(II)), both the singlet-excited state and the Eu(III) emission were quenched ("switched off"), whereas in the ground state, an MLCT band was formed, signifying the formation of stable mixed linear trimetallic f-d supramolecular self-assemblies.
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http://dx.doi.org/10.1021/ol060752j | DOI Listing |
Inorg Chem
December 2024
Department of Chemistry, Ångström Laboratory, Uppsala University, 75120 Uppsala, Sweden.
The reduction of stable trivalent lanthanide species (Ln(III)) by the excited states of organic chromophores is the basis of photocatalytic divalent lanthanide-mediated reduction reactions. While indirect evidence of the photochemical formation of the reactive Ln(II) species is abundant, direct spectroscopic evidence of their presence is scarce. Here, nine chromophores with absorptions covering the near UV and visible ranges were systematically investigated in the presence of Ln(III) ions to evaluate their ability to reduce Eu(III) upon excitation with visible light to the catalytically active Eu(II) species.
View Article and Find Full Text PDFACS Omega
December 2024
Department of Chemistry, Faculty of Science, Chiang Mai University, 239 Houy Kaew Road, Chiang Mai 50200, Thailand.
To examine the water-induced photoluminescence turn-on and its potential application in trace water sensing, a new series of [Ln(dmba)(HO)]·2HO, where Ln = La (), Pr (), Nd (), Sm (), Eu (), Gd (), Tb (), Dy (), Ho (), and Er (), were synthesized using dimethoxybenzoic acid (Hdmba). Their single-crystal structures and thermal and chemical robustness were investigated, and the effects of lanthanide contraction and noncovalent interactions were discussed. The photoluminescence and colorimetric properties of - were investigated.
View Article and Find Full Text PDFInorg Chem
November 2024
Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong 518055, China.
Chiral metal halide materials are emerging chiroptical materials that are easy to synthesize and have a wide tunability. Rare-earth (RE) metals are desirable components to be incorporated in the hybrid regime; however, they are typically difficult to handle for solution-based halide chemistry. Here, we report two new examples of chiral RE metal halides with Ce(III) and Eu(III) with chiral alkanolammonium cations (/-3-hydroxyquinuclidium).
View Article and Find Full Text PDFInorg Chem
November 2024
Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S Cass Ave, Lemont, Illinois 60439, United States.
A fundamental understanding of coordination chemistry across the lanthanide series is essential for explaining the chemical behavior of rare-earth metals in complex liquid-liquid extraction processes. Probing the exact bonding between the extractant and the metal is sometimes done through the synthesis of solid-state compounds that can serve as models for metal speciation in solution. In the case of diglycolamide (DGA), a commonly used neutral diamide extractant, extensive studies identify the stepwise formation of 1:1 [Ln(DGA)(HO)], 1:2 [Ln(DGA)(HO)], and 1:3 [Ln(DGA)] complexes in solution.
View Article and Find Full Text PDFDalton Trans
November 2024
Advanced Materials Group, Materials Sciences & Technology Division, CSIR-North East Institute of Science and Technology, Jorhat-785006, Assam, India.
A new set of metal-organic frameworks was designed by functionalizing g-CN with benzoic acid and using them as structure-directing ligands during the metal-organic framework (MOF) formation. One such MOF exhibited dual emissions, both metal- and ligand-centered, enabling ratiometric sensing of the carcinogenic industrial solvent dioxane. The fabricated MOFs possessed a unique fluffy spherical morphology that enabled atomic level resolution in transmission electron microscopy-a rarity in MOFs due to the 'Knock-on' effect.
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