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The reaction of Ln(NO3)2·6H2O (Ln = Nd, Sm, Eu, Tb, Dy, Tm and Yb) with the respective enantiopure (R)-(−)-2-phenylbutyric or (S)-(+)-2-phenylbutyric acid (R/S-2-HPhBut) and 4,7-diphenyl-1,10-phenanthroline (Bphen) allows the isolation of chiral dinuclear compounds of the formula [Ln2(μ-R/S-2-PhBut)4(R/S-2PhBut)2(Bphen)2] where Ln = Nd3+ (R/S-Nd-a), Sm3+ (R/S-Sm-a), Eu3+ (R/S-Eu-a), Tb3+ (R/S-Tb-a and R/S-Tb-b), Dy3+ (R/S-Dy-a and R/S-Dy-b), Tm3+ (R/S-Tm-b) and Yb3+ (R/S-Yb-b). Single crystal X-ray diffraction was performed for compounds S-Eu-a and S-Tm-b. Powder crystal X-ray diffraction was performed for all complexes. From the crystallographic data two different structural motifs were found which are referred to as structure type a and structure type b. In structure type a, the Ln3+ atoms are bridged through four R or S-2-PhBut ligands with two different kinds of coordination modes whereas in structure type b the two Ln3+ atoms are bridged through four R or S-2-PhBut ligands showing only one kind of coordination mode. For those lanthanide ions exhibiting both structure types, Tb3+ and Dy3+, a difference in the luminescence and magnetism behavior is observed. All compounds (except R/S-Tm-b) exhibit sensitized luminescence, notably the Eu3+ and Tb3+ analogues. Circular Dichroism (CD) and Circular Polarized Luminescence (CPL) in the solid state and in 1 mM dichloromethane (DCM) solutions are reported, leading to improved chiroptical properties for the DCM solutions. The asymmetry factor (glum) in 1 mM DCM is ±0.02 (+ for R-Eu-a) for the magnetically allowed transition 5D0 → 7F1 and ±0.03 (+ for R-Tb-a and R-Tb-b) for the 5D4 → 7F5 transition. Magnetic properties of all compounds were studied and the Dy3+ compound with the structural motif b (R-Dy-b) shows Single Molecular Magnet (SMM) behavior under a 0 T magnetic field. However, R-Dy-a is a field-induced SMM. [ABSTRACT FROM AUTHOR]

Five new β-diketonate Ce3+ mononuclear complexes, [Ce(Btfa)3(H2O)2] (1), [Ce(Btfa)3(phen)] (2), [Ce(Btfa)3(bipy)] (3), [Ce(Btfa)3(terpy)] (4) and [Ce(Btfa)3(bathophen)(DMF)] (5), where Btfa− = 4,4,4-trifluoro-1-phenyl-1,3-butanedionate, phen = 1,10-phenanthroline, bipy = 2,2′-bipyridyl, terpy = 2,2′:6′,2′′-terpyridine and bathophen = 4,7-diphenyl-1,10-phenanthroline, have been synthesized and structurally characterized through X-ray diffraction of single crystals. The central Ce3+ atom displays a coordination number of 8 for 1, 2 and 3 and of 9 for 4 and 5. Under a 0 T external magnetic field, none of the given compounds exhibits single molecule magnet (SMM) behaviour. However, a small magnetic field, between 0.02 and 0.1 T, is enough for all the compounds to exhibit slow relaxation of the magnetization. A comprehensive magnetic analysis, with experimental magnetic data and ab initio calculations, was undertaken for all the complexes, and the study highlights the significance of the different spin relaxation mechanisms that must be considered for a Ce3+ lanthanide ion. [ABSTRACT FROM AUTHOR]

The reaction of Ln(NO3)2·6H2O (Ln = Eu, Tb, Dy and Sm) with (R)-(−)-α-methoxyphenylacetic acid (R-HMPA) and 1,10-phenanthroline (phen) in EtOH/H2O allows the isolation of 1D chiral compounds of formula [Ln(μ-R-MPA)(R-MPA)2(phen)]n in which Ln = Eu (R-Eu), Tb (R-Tb), Dy (R-Dy) and Sm (R-Sm). The same synthesis by using (S)-(+)-α-methoxyphenylacetic acid (S-HMPA) instead of (R)-(−)-α-methoxyphenylacetic acid allows the isolation of the enantiomeric compounds with formula [Ln(μ-S-MPA)(S-MPA)2(phen)]n where Ln = Eu (S-Eu), Tb (S-Tb), Dy (S-Dy) and Sm (S-Sm). Single crystal X-Ray diffraction measurements were performed for compounds R/S-Eu , R/S-Tb , S-Dy and S-Sm. The luminescence and the circular dichroism measured in the solid state are reported. All compounds show sensitized luminescence, notably the Eu3+ and Tb3+ ones, whose emission color can be perceived by the naked eye. For the Eu3+ and Tb3+ derivatives the quantum yield and the circular polarized luminescence have been measured. For the magnetic allowed transition 5D0 → 7F1 of the Eu3+ compound, the anisotropy factor glum is ±0.013 (+for S-Eu). Also, magnetic properties of all compounds were studied with the Dy3+ analogue showing slow relaxation of the magnetization under a direct current magnetic field of 1000 Oe. [ABSTRACT FROM AUTHOR]

The reaction of LnCl3·6H2O with (S)-(+)-2-(6-methoxy-2-naphthyl)propionic acid (S-HL), best known as naproxen, and 1,10-phenanthroline (phen) in EtOH allows the isolation of dinuclear chiral compounds S-1–4 of the formula [Ln2(S-L)6(phen)2]·3DMF·H2O [Ln(iii) = Eu (1), Gd (2), Tb (3) and Dy (4)]. The use of the R-enantiomeric species of the HL ligand led to complexes R-1–4 with the formula [Ln2(R-L)6(phen)2]·3DMF·H2O. Compounds R- andS-1, 3 and 4 show strong sensitized metal-centred luminescence in the visible region. Moreover, Dy(iii) complexes R- andS-4 display field-induced single-molecule magnet (SMM) behaviour. For chiral and emissive compounds circularly polarized luminescence (CPL) measurements have also been performed. [ABSTRACT FROM AUTHOR]

The reaction of Ln(NO3)2·6H2O (Ln = Tb and Eu) with (S)-(+)-2-phenylpropionic acid (S-HL) and 1,10-phenanthroline (phen) in EtOH/H2O allows the isolation of the dinuclear chiral compounds of the formula [Ln2(S-L)6(phen)2]·2.5·S-HL in which Ln = Tb (S-1), Ln = Eu (S-2). The same synthesis by using (R)-(−)-2-phenylpropionic acid (R-HL) instead of (S)-(+)-2-phenylpropionic acid allows the isolation of the enantiomeric compounds with the formula [Ln2(R-L)6(phen)2]·2.5·R-HL where Ln = Tb (R-1), Ln = Eu (R-2). All compounds show sensitized luminescence. The luminescence study, including the circularly polarized luminescence spectra of the four compounds, is reported. The magnetic behavior of S-1 and S-2 is also reported. [ABSTRACT FROM AUTHOR]

The reaction of Ni(NO3)2·6H2O with di-2-pyridyl ketone, (py)2CO, and the R-phenylcyanamides 4Cl-3CF3-PhHNCN and 4F-3CF3-PhHNCN in CH3OH or CH3CH2OH allows the isolation of the tetranuclear compounds [(Ni4(μ-py2COOCH3)2(μ3-py2COOH)2(μ1,1-4Cl-3CF3-PhNCN)2(4Cl-3CF3-PhNCN)2]·CH3OH (1), [(Ni4(μ-py2COOCH2CH3)2(μ3-py2COOH)2(μ1,1-4Cl-3CF3-PhNCN)2(4Cl-3CF3-PhNCN)2]·2EtOH (2) and [(Ni4(μ-py2COOCH3)2(μ3-py2COOH)2(μ1,1-4F-3CF3-PhNCN)2(4F-3CF3-PhNCN)2]·4CH3OH (3). {(py)2C(OH)O}− and {(py)2C(OR)O}− are the monoanions of the gem-diol and hemiketal (R = CH3, CH2CH3) forms of (py)2CO. X-ray diffraction analysis reveals defective double-cubane tetrameric entities in which the Ni(ii) atoms are linked by μ1,1-R-phenylcyanamido bridges and two kinds of O-bridges. The molar magnetic susceptibility measurements of 1–3 in the 2–300 K range indicate bulk ferromagnetic coupling. [ABSTRACT FROM AUTHOR]

The syntheses and structural characterization of three new monodimensional azido-bridged manganese(ii) complexes with empirical formulae [Mn(N3)2(aminopyz)2]n (1), [Mn(N3)2(4-azpy)2]n (2) and [Mn(N3)2(4-Bzpy)2]n (3) (pyz = pyrazine (1,4-diazine)), 4-azpy = 4-azidopyridine and 4-Bzpy = 4-benzoylpyridine) are reported. 1 is a monodimensional compound with double EO azido bridges, 2 is an alternating monodimensional compound with double end-on and double end-to-end azido bridges in the sequence di-EO-di-EE and 3 is a monodimensional compound with double end-on and double end-to-end azido bridges in the sequence di-EO-di-EO-diEO-di-EO-di-EE. The magnetic properties of 1–3 are reported. Periodic DFT calculations were performed to estimate the J values and quantum Monte Carlo simulations were carried out using the calculated J values to check their accuracy in comparison with the experimental magnetic measurements. From this theoretical analysis, two appealing features of the di-EO Mn(ii) compounds can be extracted: first, the exchange coupling becomes more ferromagnetic when the Mn–N–Mn bridging angle becomes larger and the spin density of the bridging nitrogen atoms has an opposite sign to that of the Mn(ii) centers. [ABSTRACT FROM AUTHOR]

Four new triangular copper(II) complexes with the fragment {Cu3(µ3-OH)(oximate)3}2+ and formulae [Cu3(µ3-OH)(µ-Cl)(Py2CNO)3(tBuPO3H)]·4H2O (1), [Cu3(µ3-OH)(µ-Br)(Py2CNO)3(tBuPO3H)]·3.5H2O (2), [Cu3(µ3-OH)(µ-Br)(PhPyCNO)3(tBuPO3H)(MeOH)]·1.5 MeOH (3), [Cu3(µ3-OH)Cl2(PhPyCNO)3]·0.5H2O (4), (Py2CNO = di(2-pyridyl)ketoximate, PhPyCNO = phenyl(2-pyridyl)ketoximate, tBuPO3H2 = tert-butylphosphonic acid) are reported. The magnetic properties of compounds 1-4 were studied. The compounds were found to exhibit strong antiferromagnetic coupling and antisymmetric exchange interaction. [ABSTRACT FROM AUTHOR]

The employment of the 1,3-bis(dimethylamino)-2-propanolate (bdmap) ligand as a chelating/bridging ligand in manganese chemistry is described. The reaction of Mn(R-BzO)2and bdmap affords [Mn8(O)4(R-BzO)12(bdmap)2(H2O)2], R = H (1), R = 3-Cl (2) and R = 4-Cl (3), which are mixed-valence MnII2MnIII6clusters. Structural characterization was achieved for 1and 2, which can be described as a central double defective dicubane MnIII4subunit, capped by two oxo-bridged MnII-μ(bdmap)-MnIIIdinuclear units. DC variable-temperature magnetic susceptibility studies were carried out in the 2–300 K range, revealing an overall antiferromagnetic behaviour for 1–3. This work demonstrates for the first time the ability of this kind of polytopic ligands in high nuclearity manganese chemistry. [ABSTRACT FROM AUTHOR]