The use of N-salicylidene-o-aminophenol (H2saph) in 4f-metal chemistry has led to the isolation of seven new isostructural lanthanide(iii) [Ln(III)] complexes. More specifically the Ln(NO3)3·xH2O/H2saph/Et3N (1 : 1 : 1) reaction mixtures in DMF/MeCN gave complexes [Ln2(NO3)2(saph)2(DMF)4] (Ln = Sm (); Eu (); Gd (); Tb (); Dy (); Ho (); Er ()) in good yields (∼65%). The structures of the isomorphous complexes and were solved by single-crystal X-ray crystallography; the other complexes are proposed to be isostructural with and based on elemental analyses, IR spectra and powder XRD patterns. The two Ln(III) atoms in the centrosymmetric molecules of and are doubly bridged by the deprotonated iminophenolato oxygen atoms of two nearly planar η(1):η(1):η(2):μ saph(2-) ligands. The imino nitrogen and five terminal oxygen atoms (the salicylaldiminate, two from one bidentate chelating nitrato group and two from two DMF ligands) complete square antiprismatic coordination at each metal centre. The IR spectra of the complexes are discussed in terms of the coordination modes of the ligands present in the complexes. Solid-state emission studies for all display identical ligand-based photoluminescence. Dc magnetic susceptibility studies in the 2-300 K range reveal the presence of a weak, intramolecular antiferromagnetic exchange interaction (J = -0.19(1) cm(-1) based on the spin Hamiltonian H = -J(ŜGd·ŜGd')) for and probably ferromagnetic exchange interaction within the molecules of and . Ac magnetic susceptibility measurements in zero dc field show temperature- and frequency-dependent out-of-phase signals with two well defined, thermally-activated processes for , suggesting potential single-molecule magnetism character. The Ueff value is 17.4 cm(-1) for the higher temperature process and 16.2 cm(-1) for the lower temperature one. The combination of photoluminescence and single-molecule behaviour in the Dy complex is critically discussed.

Reactions of FeIII sources with 2‐pyridyl oxime ligands, pyC(R)NOH (R=H, Me, Ph), afforded the trinuclear oxo‐centered complexes (NH4)[Fe3O(LH)6(H2O)3](ClO4)8 ⋅MeOH⋅1.14H2O (1⋅ MeOH⋅1.14H2O) and [Fe3O{pyC(H)NO)(PhCO2)6(H2O)]⋅MeCN (2⋅MeCN), the tetranuclear complex [Fe4(OH)4{pyC(Me)NO}4(H2O)4] (ClO4)4⋅3Me2CO⋅H2O (3⋅3Me2CO⋅H2O), and the hexanuclear complexes [Fe6(OH)6{pyC(Me)NO}6(H2O)6](ClO4)6⋅8Me2CO⋅2H2O (4⋅8Me2CO⋅2H2O), [Fe6(OH)6{pyC(Me)NO}6(MeCONH2)6](ClO4)6⋅2MeCN⋅H2O (5⋅2MeCN⋅H2O), [Fe6(OH)6 {pyC(Ph)NO}6(H2O)6](ClO4)6⋅4.4Me2CO ⋅1.6Et2O (6⋅4.4Me2CO ⋅1.6Et2O) and [Fe6(OH)6{pyC(Ph)NO}6(MeOH)6](ClO4)5.5(OH)0.5⋅MeOH⋅0.5H2O (7⋅MeOH ⋅0.5H2O), where LH is the zwitterion anionic form of 2‐pyridinecarboxylic acid (picolinic acid). Complex 3 can be described as inverse 12‐metallacrown‐4, whereas 4–7 can be described as inverse 18‐metallacrowns‐6 and represent the first examples of iron(III) metallacyclic clusters with pyC(R)NOH (R=H, Me, Ph) ligands. Complexes 3 and 6 were characterized by Mössbauer spectroscopy and magnetic susceptibility measurements, while complex 2 was characterized by EPR spectroscopy.

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Reactions of methyl-2-pyridyl ketone, pyCOMe, with FeCl3·6H2O in various solvents gave complexes [Fe4Cl6(OMe)2(L1)2]·0.7MeCN·0.4MeOH (1·0.7MeCN·0.4MeOH) and [Fe3Cl4(bicine)(L2)]·Me2CO·0.2H2O (2·Me2CO·0.2H2O). The ligands (L1)2- = pyCO(Me)CH=COpy (in 1) and (L2)2- = pyCO(Me)CH2CO(OMe)py (in 2)...