Synthesis, Crystal Structures and Magnetic Properties of Trinuclear {Ni2Ln} (LnIII = Dy, Ho) and {Ni2Y} Complexes with Schiff Base Ligands

The reaction of the Schiff base ligand o-OH-C6H4-CH=N-C(CH2OH)3, H4L, with Ni(O2CMe)2∙4H2O and lanthanide nitrate salts in a 4:2:1 ratio lead to the formation of the trinuclear complexes [Ni2Ln(H3L)4(O2CMe)2](NO3) (Ln = Dy (1), Ho (2), and Y (3)) which crystallize in the non-centrosymmetric space group Pna21. The complex cation consists of the three metal ions in an almost linear arrangement. The {Ni2Ln} moieties are bridged through two deprotonated Ophenolato groups from two different ligands. Each terminal NiII ion is bound to two ligands through their Ophenolato, the Nimino atoms and one of the protonated Oalkoxo groups in a distorted octahedral. The central lanthanide ion is coordinated to four Ophenolato oxygen from the four ligands, and four Ocarboxylato atoms from two acetates which are bound in the bidentate chelate mode, and the coordination polyhedron is biaugmented trigonal prism, which probably results in a non-centrosymmetric arrangement of the complexes in the lattice. The magnetic properties of 1–3 were studied and showed that 1 exhibits field induced slow magnetic relaxation.

Field-Induced SMM and Vis/NIR Luminescence on Mononuclear Lanthanide Complexes with 9-Anthracenecarboxylate and 2,2′:6,2″-Terpyridine

Five new mononuclear lanthanide complexes are synthesized by adding the several lanthanide nitrate hexahydrate salts, which for lanthanide (Ln) are Eu, Tb, Dy, Er, and Yb, with 9-anthracenecarboxylic acid (9-Hanthc) and 2,2′:6,2″-terpyridine (TPY) in mixed solution of methanol and dimethylformamide (DMF). The general formula is [Eu(9-anthc)3(TPY)(DMF)]·H2O (1Eu) where Eu(III) is ennea-coordinated or [Ln(9-anthc)3(TPY)(H2O)]·H2O·DMF (Ln = Tb (2Tb), Dy (3Dy), Er (4Er), and Yb (5Yb)) where Ln(III) is octa-coordinated. For compounds 3Dy, 4Er, and 5Yb, the dynamic ac magnetic study indicated field-induced single molecule magnet (SMM) behavior. The photoluminescence studies in the solid state of these complexes show the sensitization of 4f-4f transitions for 4Er and 5Yb in the NIR region.

Novel lanthanide(III) 4-methylbenzoylhydrazide complexes as precursors for lanthanide oxide nanophotocatalysts

A series of metal complexes were prepared from separate reactions of lanthanide nitrate salts (La(iii), Ce(iii), Sm(iii), Gd(iii) and Ho(iii)) with 4-methylbenzoylhydrazide.

Magnetic and luminescent coordination networks based on imidazolium salts and lanthanides for sensitive ratiometric thermometry

The synthesis and characterization of six new lanthanide networks [Ln(L)(ox)(H2O)] with Ln = Eu3+, Gd3+, Tb3+, Dy3+, Ho3+ and Yb3+ is reported. They were synthesized by solvo-ionothermal reaction of lanthanide nitrate Ln(NO3)3·xH2O with the 1,3-bis(carboxymethyl)imidazolium [HL] ligand and oxalic acid (H2ox) in a water/ethanol solution. The crystal structure of these compounds has been solved on single crystals and the magnetic and luminescent properties have been investigated relying on intrinsic properties of the lanthanide ions. The synthetic strategy has been extended to mixed lanthanide networks leading to four isostructural networks of formula [Tb1− x Eu x (L)(ox)(H2O)] with x = 0.01, 0.03, 0.05 and 0.10. These materials were assessed as luminescent ratiometric thermometers based on the emission intensities of ligand, Tb3+ and Eu3+. The best sensitivities were obtained using the ratio between the emission intensities of Eu3+ (5D0→7F2 transition) and of the ligand as the thermometric parameter. [Tb0.97Eu0.03(L)(ox)(H2O)] was found to be one of the best thermometers among lanthanide-bearing coordination polymers and metal-organic frameworks, operative in the physiological range with a maximum sensitivity of 1.38%·K−1 at 340 K.

Tetraaqua[2,6-diacetylpyridine bis(semicarbazone)]samarium(III) trinitrate

The structure of tetraaqua[2,6-diacetylpyridine bis(semicarbazone)]samarium(III) trinitrate, [Sm(C11H15N7O2)(H2O)4](NO3)3, has monoclinic (P21/c) symmetry. The 2,6-diacetylpyridine (DAPSC) ligand is pentadentate. The coordination of the DAPSC ligand and four coordinated water molecules around the metal cation is best described as a distorted tricapped trigonal prism. The structure displays intermolecular hydrogen bonding. The structure is isomorphous with many other published lanthanide(III) nitrate salts with the DAPSC ligand, 2,6-diacetylpyridinebis(semicarbazone). One of the three nitrate counter-anions is disordered, which is consistent with the structures of other +3 lanthanide nitrate salts with DAPSC. Refinement of occupancies for the disordered nitrate group gave major and minor occupancies of 54.9 (14) and 45.1 (14)%, respectively.

Unusual complexation of nitrate with lanthanides in a wet ionic liquid: a new approach for aqueous separation of trivalent f-elements using an ionic liquid as solvent

The energetics of lanthanide nitrate complexation in a wet ionic liquid (IL; saturated with water as seen in the aqueous separation process) differs entirely from that in dry IL.