A series of dinuclear lanthanide complexes incorporating the 2-ethoxycinnamate ligand have been synthesized and characterized using elemental analyses, infra-red spectroscopy, X-ray diffraction and magnetic measurements. Depending on the nature of the lanthanide ion, three different isostructural series of respective formulas, [Ln(L)3(DMSO)(H2O)]2 (Ln = Ce (1), Nd (2)), [Ln(L)3(DMSO)x(DMF)y(H2O)]2 (Ln = Gd (3), Dy (5) and Er (6)) and [Tb(L)3(DMF)(H2O)]2 (4) have been obtained. Investigations of their magnetic properties reveal a genuine single-molecule magnet behaviour observed for the dysprosium based compound 5, while a field-induced slow relaxation of the magnetization is found for compounds 1, 2 and 3.
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http://dx.doi.org/10.1039/c8dt03020k | DOI Listing |
Molecules
December 2024
Dipartimento di Scienze Chimiche e Geologiche, Università di Cagliari, Complesso Universitario di Monserrato, S.P. 8 Km 0.700, I-09042 Monserrato, Italy.
By combining Er and Yb ions with 3,6-dithiophene-anilate (ThAn) and scorpionate hydrotris(pyrazol-1-yl)borate (HBpz) ligands new luminescent dinuclear complexes are obtained. The two materials formulated as [((HB(pz))Yb)(μ-thAn)]·4DCM·1.3HO and [((HB(pz))Er)(μ-thAn)]·4DCM·1.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Univ Brest, UMR CNRS 6521-, Laboratoire CEMCA, F 29200, Brest, France.
Ligands combining two lateral bis-pyridyl-phosphonated-pyclens were synthesized, using a flexible linear pegylated linker (L2) or a bulkier K22 crown-ether (L3). A functionalized pyridyl-phosphonated-pyclen (L1) was also prepared as a mononuclear analogue. Coordination behavior of lanthanide cations was studied via NMR titration with Lu for L1, and UV/Vis and luminescence spectroscopy with Yb for L2/L3.
View Article and Find Full Text PDFMolecules
November 2024
G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 49 Tropinina Str., GSP-445, 603950 Nizhny Novgorod, Russia.
The coordination environment of magneto-luminescent Dy-based Single-Molecule Magnets (SMM) is a crucial factor influencing both magnetic and luminescent properties. In this work, we explore how triphenylmethanolate (PhCO), in combination with other ligands, can modulate the structure and, therefore, the magnetic properties of Dy-based SMM. Using triphenylmethanolate in combination with THF and pyridine (Py) as co-ligands, we synthesized a series of mononuclear -[Dy(OCPh)(THF)][BPh]·(2,6-MeCHN) (), -Dy(OCPh)(THF) (), -Dy(OCPh)(py) () and dinuclear [(PhCO)Dy(THF){(μ-Cl)Li(THF)}μ-Cl] () complexes where the Dy ion presents five- or six-coordinate geometries.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Department of Chemistry and Key University Laboratory of Rare Earth Chemistry of Guangdong, Southern University of Science and Technology, Shenzhen, 518055, China.
Lanthanide-containing clusters are synthetically challenging and with significant chemical and materials applications. Herein, two isostructural heterometallic clusters of the formula (NO)@[LnNi(OH)(IDA)(CHCOO)(NO)(HO)]Cl⋅xHO⋅yCHOH (IDA=iminodiacetate; Ln=Gd 1, x=110, y=0; Ln=Eu 2, x=95, y=40) were obtained via co-hydrolysis of Ln (Gd or Eu) and Ni in the presence of iminodiacetate (IDA). Crystallographic studies show that each features a truncated tetrahedral core of LnNi within which a void of 1.
View Article and Find Full Text PDFJ Am Chem Soc
October 2024
EaStCHEM School of Chemistry, University of Edinburgh, EH9 3FJ, Edinburgh, United Kingdom.
The analysis of intervalence charge transfer (IVCT) in mixed-valence compounds can help understand electron transfer processes that are important in diverse applications such as molecular electronics and artificial photosynthesis. While mixed-valence complexes of the lanthanides are more difficult to access than their transition metal analogues, they have shown IVCT phenomena derived from Robin-Day Class II localized valency or even electronic transitions due to - metal-metal bonding. In contrast, we report here the synthesis, characterization, and computational analysis of a rare, Robin-Day Class III, singly reduced dinuclear Yb complex, which is best viewed as having delocalized oxidation states.
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