Levamisole based Co(II) Single-Ion Magnet.

A new Co(II) complex, [Co(NCS)2(L)2] (1) has been synthesized based on levamisole (L) as a new ligand. Single-crystal X-ray diffraction analyses confirm that the Co(II) ion is having a distorted tetrahedral coordination geometry in the complex. Notably strong intramolecular S∙∙∙S and S∙∙∙N interactions has been confirmed by employing Quantum Theory of Atoms in Molecules (QTAIM). These intramolecular interactions occur among the sulfur and nitrogen atoms of the levamisole ligands and also the nitrogen atoms of the thiocyanate. Direct current (dc) magnetic analyses reveal presence of zero field splitting (ZFS) and large magnetic anisotropy on Co(II). Detailed ab initio ligand field theory calculations quantitatively predicted the magnitude of ZFS. Prominent field-induced single-ion magnet (SIM) behavior was observed for 1 from dynamic magnetization measurements. Slow magnetic relaxation follows an Orbach mechanism with the effective energy barrier Ueff = 29.6 (7) K and relaxation time to = 1.4 (4) × 10-9 s.

Exploration of SMM behavior of Ln2 complexes derived from thianaphthene-2-carboxylic acid.

Two lanthanide-based dinuclear complexes [LnIII(L)3(DMF)(H2O)]2 (Ln = DyIII (1)/TbIII (2)) derived from thianaphthene-2-carboxylic acid have been synthesized and characterized in detail. Single-crystal XRD analyses confirm that the centro-symmetric discrete dimeric structures contain eight-coordinated lanthanide centers with biaugmented trigonal prism geometry in the complexes. Magnetic studies reveal the presence of antiferromagnetic interaction as well as thermal depopulation of Stark sublevels with a decrease in temperature for both complexes, whereas prominent field-induced single-molecule magnet behavior was observed for 1. Also, an isostructural yttrium-based complex (3) and a magnetically dilute sample of complex 1 (1') have been prepared for magnetic dilution study. 1' shows a combination of Orbach and Raman relaxation processes with effective energy barrier ΔE = 19.508 cm-1 and relaxation time τo = 9.710 × 10-10 s.

Anion-driven structures and SMM behavior of dinuclear terbium and ytterbium complexes.

The work in this present investigation reports the syntheses, crystal structures and magnetic properties of five dinuclear lanthanide complexes having compositions [Tb2(HL)4(NO3)6] (1), [Tb2(HL)4Cl6]·2EtOH (2), [Yb2(HL)4(NO3)6] (3), [Yb2(HL)4Cl6]·2EtOH (4) and [Y2(HL)4(NO3)6] (5) with HL = 8-hydroxyquinaldine. It is evident from the crystal structures that the coordination number of trivalent lanthanide ions in compounds 1, 3 and 5 is nine, whereas that for compounds 2 and 4 is six. A dynamic magnetic study shows that both compounds 1 and 3 exhibit single-molecule-magnet (SMM) behavior while compounds 2 and 4 do not have any SMM property.

Syntheses, crystal structures and steady state and time-resolved fluorescence properties of a PET based macrocycle and its dinuclear ZnII/CdII/HgII complexes.

The work in the present investigation reports the syntheses, crystal structures, ESI-MS (positive) and steady state and time resolved photophysical properties of a tetraaminodiphenol macrocyclic ligand H2L (saturated analogue of a tetraiminodiphenol macrocycle obtained on 2 + 2 condensation of 4-ethyl-2,6-diformylphenol and 2,2-dimethyl-1,3-diaminopropane) and its three dinuclear d10 metal ion (ZnII, CdII and HgII) complexes having compositions [ZnLCl2]·2CH3OH (1), [CdL(µ-H2O)(H2O)2](NO3)2·4H2O (2) and [HgLCl2] (3). H2L is colorless and weakly fluorescent, Cd compound 2 is colorless and more weakly fluorescent, Zn compound 1 is colorless and highly fluorescent and Hg compound 3 is yellow and nonemissive. The order of the radiative rate constant (Kr), obtained from time-resolved studies, corroborates the order of quantum yields, obtained from steady state studies: 1 (φ = 0.12; Kr = 116.6 × 106 s-1) ≫ H2L (φ = 0.005; Kr = 7.726 × 106 s-1) > Cd compound 2 (φ = 0.0014; Kr = 0.675 × 106 s-1). Spectrophotometric and steady state/time-resolved spectrofluorimetric titrations of H2L with ZnII, CdII and HgII have been performed. The relative fluorescence efficiencies of H2L, H2L + various single metal ions (ZnII, CdII, HgII, CuII, NiII, CoII, FeII, MnII) and H2L + ZnII + another metal ion (metal ion competition study) have been studied. Relative fluorescence efficiency can be well rationalized in terms of photoinduced electron transfer (PET), perturbation of PET by metal coordination (chelation enhanced fluorescence, CHEF), heavy metal ion effect (spin-orbit coupling) and fluorescence quenching mechanism. It has been established from comparative fluorescence spectra of 4-ethylphenol, H2L and 1 that H2L can be reasonably considered as a PET species in which the fluorophore is 4-ethylphenol. The binding constants, as determined from titration experiments, qualitatively corroborate the results of metal ion competition studies. The modulation of the absorption spectra and color of the H2L-HgII solution in the presence of various diamagnetic metal ions has been explored. Significant aspects of structures and spectroscopic properties have been discussed.

Unprecedented dinuclear Robson type macrocyclic complexes having two +iii metal ions in two compartments and the role of the diimino moiety on the stability of metal ion oxidation states.

The work in this investigation deals with the syntheses, characterization, crystal structures and catechol oxidase activity of four diphenoxo-bridged Co(III)Co(III) compounds of composition [Co(III)Co(III)L(Me-pn)(N3)4]·6H2O (), [Co(III)Co(III)L(Me-pn)(N3)4]·4H2O (), [Co(III)Co(III)L(Et-pn)(N3)4]·3.5H2O () and [Co(III)Co(III)L(Et-pn)(N3)4]·CH3CN·2.5H2O (), and two diphenoxo-bridged Co(III)Co(II) compounds of composition [Co(III)Co(II)L(Me-Me2pn)(N3)3]·2H2O () and [Co(III)Co(II)L(Et-Me2pn)(N3)3]·H2O (). In these compounds, H2L(Me-pn), H2L(Et-pn), H2L(Me-Me2pn) and H2L(Et-Me2pn) are four Robson type tetraiminodiphenolate macrocyclic ligands, in which the superscript Me and Et indicate that the dialdehyde components are 4-methyl-2,6-diformyl-phenol and 4-ethyl-2,6-diformyl-phenol, respectively, while pn and Me2pn indicate that the diamine components are 1,3-diaminopropane and 2,2-dimethyl-1,3-diaminopropane, respectively. The Co(III)Co(III) compounds are further characterized by (1)H NMR spectra. Compounds and are prepared following a metal-templated synthesis, while compounds and are prepared by direct synthesis, which includes using a pre-isolated macrocycle, [H4L(Me-pn)](ClO4)2/[H4L(Et-pn)](ClO4)2, as a reactant. On changing the diamine component of the corresponding macrocycle from 1,3-diaminopropane to 2,2-dimethyl-1,3-diaminopropane, but otherwise following the similar reaction procedure (both direct and template), the Co(III)Co(II) compounds [Co(III)Co(II)L(Me-Me2pn)(N3)3]·2H2O (), [Co(III)Co(II)L(Et-Me2pn)(N3)3]·H2O (), [Co(III)Co(II)L(Me-Me2pn)(N3)3]·0.5MeCN·0.27H2O (; Inorg. Chim. Acta, 2014, 412, 38) and [Co(III)Co(II)L(Et-Me2pn)(N3)3]·MeCN (; Dalton Trans., 2013, 42, 4561) are formed, rather than Co(III)Co(III) compounds. Like compounds and , all the compounds show catechol oxidase activity (substrate: 3,5-di-tert-butyl catechol). The kinetic parameters for , and have been determined. Their Kcat values are, respectively, 212.6, 188.0 and 191.3 h(-1). ESI-MS (positive) spectra of some representative cases (with and without the substrate) have been recorded and the positive species have been assigned well. Unprecedented and surprising aspects of the composition/structure and properties of the complexes in this investigation have been discussed.

Syntheses, structures, and steady state and time resolved photophysical properties of a tetraiminodiphenol macrocyclic ligand and its dinuclear zinc(II)/cadmium(II) complexes with coordinating and noncoordinating anions.

The work in the present investigation reports the syntheses, structures, steady state, and time-resolved photophysical properties of a tetraiminodiphenol macrocyclic ligand H(2)L and its eight dinuclear zinc(II) complexes and one cadmium(II) complex having composition [Zn(2)L(H(2)O)(2)](ClO(4))(2)·2CH(3)CN (1), [Zn(2)L(H(2)O)(2)](ClO(4))(2)·2dmf (2), [Zn(2)L(H(2)O)(2)](NO(3))(2)·2dmf (3), [Zn(2)LCl(2)] (4), [Zn(2)L(N(3))(2)] (5), [Zn(2)L(NCS)(2)] (6), [Zn(2)L(NCO)(2)] (7), [Zn(2)L(NCSe)(2)](2)·dmf (8), and [Cd(2)L(OAc)(2)] (9) with various coordinating and noncoordinating anions. The structures of all the complexes 1-9 have been determined by single-crystal X-ray diffraction. The noncovalent interactions in the complexes result in the generation of the following topologies: two-dimensional network in 1, 2, 4, 6, 7, 8, and 9; three-dimensional network in 5. Spectrophotometric and spectrofluorometric titrations of the diprotonated salt [H(4)L](ClO(4))(2) with triethylamine as well as with zinc(II) acetate and cadmium(II) acetate have been carried out, revealing fluorescence enhancement of the macrocyclic system by the base and the metal ions. Steady state fluorescence properties of [H(4)L](ClO(4))(2) and 1-9 have been studied and their quantum yields have been determined. Time resolved fluorescence behavior of [H(4)L](ClO(4))(2) and the dizinc(II) and dicadmium(II) complexes 1-9 have also been studied, and their lifetimes and radiative and nonradiative rate constants have been determined. The induced fluorescence enhancement of the macrocycle by zinc(II) and cadmium(II) is in line with the greater rate of increase of the radiative rate constants in comparison to the smaller rate of increase of nonradiative rate constants for the metal complexes. The fluorescence decay profiles of all the systems, being investigated here, that is, [H(4)L](ClO(4))(2) and 1-9, follow triexponential patterns, revealing that at least three conformers/components are responsible to exhibit the fluorescence decay behavior. The systems and studies in this report have been compared with those in the reports of the previously published similar systems, revealing some interesting aspects.