The reaction of (S)P[N(CH3)NCH-C6H3-2-OH-3-OCH3]3 with a MnII salt followed by a LnIII salt (Ln = Eu, Gd and Dy), afforded linear heterometallic complexes [L2Mn2Ln]+ that showed interesting magnetic properties.

The reaction of (S)P[N(CH3)NCH-C6H3-2-OH-3-OCH3]3 with a MnII salt followed by a LnIII salt (Ln = Eu, Gd and Dy), afforded linear heterometallic complexes [L2Mn2Ln]+ that showed interesting magnetic properties.

The sequential reaction of a phosphorus-based trishydrazone ligand, LH3 with anhydrous ZnCl2 and LnCl3·6H2O in a 2:2:1 stoichiometric ratio in the presence of triethylamine as the base leads to the formation of monocationic trinuclear complexes [L2Zn2Ln]Cl {Ln = Gd (1), Tb (2), Nd (3), Eu (4) and L = [(S)P[N(Me)NCH–C6H3-2-O-3-OMe]3}. All the three metal ions, in each of these compounds, are arranged in a linear fashion. The two terminal Zn(II) ions are encapsulated by three imino and three phenolate oxygen atoms while the lanthanide ion remains in the centre with an all-oxygen coordination environment. Detailed photophysical measurements reveal the complete absence of antenna sensitization in all the four complexes. However, a strong emission was found for 2 and 4 when excited directly at their f–f levels.

The sequential reaction of a phosphorus-based trishydrazone ligand, LH3 with anhydrous ZnCl2 and LnCl3·6H2O in a 2:2:1 stoichiometric ratio in the presence of triethylamine as the base leads to the formation of monocationic trinuclear complexes [L2Zn2Ln]Cl {Ln = Gd (1), Tb (2), Nd (3), Eu (4) and L = [(S)P[N(Me)NCH–C6H3-2-O-3-OMe]3}. All the three metal ions, in each of these compounds, are arranged in a linear fashion. The two terminal Zn(II) ions are encapsulated by three imino and three phenolate oxygen atoms while the lanthanide ion remains in the centre with an all-oxygen coordination environment. Detailed photophysical measurements reveal the complete absence of antenna sensitization in all the four complexes. However, a strong emission was found for 2 and 4 when excited directly at their f–f levels.

Sequential reaction of LH3 (LH3 = (S)P[N(Me)N═CH−C6H3-2-OH-3-OMe]3) with Co(OAc)2·4H2O followed by reaction with lanthanide salts afforded trinuclear heterobimetalllic compounds {[L2Co2Ln][X]} [Ln = Eu (1), X = Cl; Ln = Tb (2), Dy (3), Ho (4), X = NO3] in excellent yields. These compounds retain their integrity in solution as determined by electrospray ionization mass spectrometry studies. The molecular structures of 1−4 were confirmed by a single-crystal X-ray structural study and reveal that these are isostructural. In all of the compounds, the three metal ions are arranged in a perfectly linear manner and are held together by two trianionic ligands, L3−. The two terminal CoII ions contain a facial coordination environment (3N, 3O) comprising three imino nitrogen atoms and three phenolate oxygen atoms. The coordination geometry about the cobalt atom is severely distorted. An all-oxygen coordination environment (12O) is present around the central lanthanide ion, which is present in a distorted icosahedral geometry. The coordination sphere around the lanthanide ion is achieved by utilizing three phenolate oxygen atoms and three methoxy oxygen atoms of each ligand. In all of these trinuclear complexes (1−4), the Co−Ln distances are around 3.3 Å, while the Co−Co distances range from 6.54 to 6.60 Å. The screw-type coordination mode imposed by the ligand induces chirality in the molecular structure, although all of the complexes crystallize as racemates. Magnetic properties of 1−4 have been studied in detail using dc and ac susceptibility measurements. Dynamic measurements reveal that 2−4 display a single-molecule magnet behavior, while the Co2Eu (1) analogue does not show any out-of-phase ac susceptibility.

The reaction of LH3 with Ni(ClO4)2·6H2O and lanthanide salts in a 2:2:1 ratio in the presence of triethylamine leads to the formation of the trinuclear complexes [L2Ni2Ln][ClO4] (Ln = La (2), Ce (3), Pr (4), Nd (5), Sm (6), Eu (7), Gd (8), Tb (9), Dy (10), Ho (11) and Er (12) and L: (S)P[N(Me)N═CH−C6H3-2-O-3-OMe]3). The cationic portion of these complexes consists of three metal ions that are arranged in a linear manner. The two terminal nickel(II) ions are coordinated by imino and phenolate oxygen atoms (3N, 3O), whereas the central lanthanide ion is bound to the phenolate and methoxy oxygen atoms (12O). The Ni−Ni separations in these complexes range from 6.84 to 6.48 Å. The Ni−Ni, Ni−Ln and Ln−Ophenolate bond distances in 2−12 show a gradual reduction proceeding from 2 to 12 in accordance with lanthanide contraction. Whereas all of the compounds (2−12) are paramagnetic systems, 8 displays a remarkable ST = 11/2 ground state induced by an intramolecular Ni· · ·Gd ferromagnetic interaction, and 10 is a new mixed metal 3d/4f single-molecule magnet generated by the high-spin ground state of the complex and the magnetic anisotropy brought by the dysprosium(III) metal ion.