Field induced single-molecule-magnet behaviour is observed for both a heterodinuclear [ZnDy(L(-))2](3+) complex (1) and a mononuclear [Dy(HL)2](3+) complex (2), with effective energy barriers of 83 cm(-1) and 16 cm(-1), respectively. Insights into the relaxation mechanism(s) and barrier heights are provided via ab initio and DFT calculations. Our findings reveal an interesting observation that the U(eff) of SMMs can be enhanced by incorporating diamagnetic metal ions.
Here, synthesis of an efficient nanocomposite based on a polyacrylamide grafted carboxymethyl tamarind (CMT-g-PAM) and a SiO2 nanoparticle is presented. The synthesized nanocomposites are characterized using FT-IR, SEM, TEM, 13C NMR, elemental analysis, viscosity, rheological measurement, and molecular weight determination. Various characterizations reveal the existence of an excellent polymer matrix–nanoparticle interaction, which is at a maximum when 1.5 wt % of SiO2 is introduced in the polymer matrix (i.e., CMT-g-PAM/SiO2-3). Nanocomposites show tremendous methylene blue (MB) dye adsorption capacity, because of their higher hydrodynamic radius as well as hydrodynamic volume, which originates from proper polymer matrix–SiO2 nanoparticle interaction. CMT-g-PAM/SiO2-3 exhibited a maximum adsorption capacity (Q max) of 43.859 mg·g–1. The adsorption behavior of the nanocomposite shows that adsorption kinetics and isotherms are in good agreement with pseudo-second-order and Langmuir equations, respectively. Negative values of ΔG° confirmed the spontaneous nature of adsorption. Further, desorption experiments affirmed that the developed nanocomposite has excellent regenerative efficacy.
A new medium, eggshell powder has been developed for fluoride removal from aqueous solution. Fluoride adsorption was studied in a batch system where adsorption was found to be pH dependent with maximum removal efficiency at 6.0. The experimental data was more satisfactorily fitted with Langmuir isotherm model. The kinetics and the factor controlling adsorption process fully accepted by pseudo-second-order model were also discussed. Eawas found to be 45.98 kJmol-1by using Arrhenius equation, indicating chemisorption nature of fluoride onto eggshell powder. Thermodynamic study showed spontaneous nature and feasibility of the adsorption process with negative enthalpy (∆H0) value also supported the exothermic nature. Batch experiments were performed to study the applicability of the adsorbent by using fluoride contaminated water collected from affected areas. These results indicate that eggshell powder can be used as an effective, low-cost adsorbent to remove fluoride from aqueous solution as well as groundwater.
Four isostructural [Ni2 Ln2 (CH3 CO2 )3 (HL)4 (H2 O)2 ](3+) (Ln(3+) =Dy (1), Tb (2), Ho (3) or Lu (4)) complexes and a dinuclear [NiGd(HL)2 (NO3 )3 ] (5) complex are reported (where HL=2-methoxy-6-[(E)-2'-hydroxymethyl-phenyliminomethyl]-phenolate). For compounds 1-3 and 5, the Ni(2+) ions are ferromagnetically coupled to the respective lanthanide ions. The ferromagnetic coupling in 1 suppresses the quantum tunnelling of magnetisation (QTM), resulting in a rare zero dc field Ni-Dy single-molecule magnet, with an anisotropy barrier Ueff of 19 K.
2D nitrile-based coordination polymer crystal shows over 110 °C of windows of liquid state and it forms a glass monolith.
Four complexes containing Dy and Pr ions and their Ln -Zn analogs have been synthesized in order to study the influence that a diamagnetic Zn ion has on the electronic structure and hence, the magnetic properties of the Dy and Pr single ions. Single-crystal X-ray diffraction revealed the molecular structures as [Dy (HL) (NO ) ] (1), [Pr (HL) (NO ) ] (2), [Zn Dy (L) (CH CO )(NO ) ] (3) and [Zn Pr (L) (CH CO ) (NO )] (4) (where HL=2-methoxy-6-[(E)-phenyliminomethyl]phenol). The dc and ac magnetic data were collected for all four complexes. Compounds 1 and 3 display frequency dependent out-of-phase susceptibility signals (χ "), which is a characteristic signature for a single-molecule magnet (SMM). Although 1 and 3 are chemically similar, a fivefold increase in the anisotropic barrier (U ) is observed experimentally for 3 (83 cm ), compared to 1 (16 cm ). To rationalize the larger anisotropic barrier (1 vs. 3), detailed ab initio calculations were performed. Although the ground state Kramer's doublet in both 1 and 3 are axial in nature (g =19.443 for 1 and 18.82 for 3), a significant difference in the energy gap (U ) between the ground and first excited Kramer's doublet is calculated. This energy gap is governed by the electrostatic repulsion between the Dy ion and the additional charge density found for the phenoxo bridging ligand in 3. This extra charge density was found to be a consequence of the presence of the diamagnetic Zn ion present in the complex. To explore the influence of diamagnetic ions on the magnetic properties further, previously reported and structurally related Zn-Dy complexes were analyzed. These structurally analogous complexes unambiguously suggest that the electrostatic repulsion is found to be maximal when the Zn-O-Dy-O dihedral angle is small, which is an ideal condition to maximize the anisotropic barrier in Dy complexes.
The reaction of hydrated nickel(II) salts (chloride or nitrate) and hydrated lanthanide nitrate salts with the Schiff base ligand 2-methoxy-6-[(E)-phenyliminomethyl] phenol (HL) in methanol resulted in the isolation of three isostructural linear heterometallic trinuclear complexes and a heterometallic tetranuclear complex. The molecular structures of these complexes were determined via single crystal X-ray diffraction revealing molecular structures of formulae [Ni2La(L-)6](NO3)0.55(OH)0.45 (1), [Ni2Pr(L-)6](NO3)0.48(OH)0.52 (2), [Ni2Tb(L-)6](NO3)0.5(Cl)0.5 (3) and [Ni2Dy2(L-2(o-vanillin)2(CO3)2(NO3)2(MeOH)2] (4). Structural analysis for 1-3 reveals that the lanthanide ion is sandwiched between two Ni(II) ions and the Ni⋯Ln⋯Ni metallic core displays a linear arrangement, with an average ∠Ni⋯Ln⋯Ni bond angle of 179.7°. Analysis of 4 reveals the metal ions are arranged such that two Ni-Dy subunits are bridged by two carbonate ligands via the Dy sites. Direct current magnetic susceptibility measurements for complexes 1-4 reveal that the Ni(II) ions are coupled ferromagnetically with the Tb(III) (3) and Dy(III) (4) ions, and antiferromagnetically with the Pr(III) ion (2). For complex 1 a long range intramolecular ferromagnetic interaction is witnessed between the Ni(II) ions (Ni⋯Ni = 6.873(9) Å) via a closed shell La(III) ion. The magnetic data of 1 were fitted using the HDVV Hamiltonian revealing the following parameters; J = +0.46 cm(-1), g = 2.245, D = +4.91 cm(-1). Alternating current magnetic susceptibility measurements performed on complexes 2-4 revealed that 3 and 4 displayed frequency dependent χ′′M signals (Hac = 3.5 Oe and Hdc = 0 Oe) which is a characteristic signature of a single-molecule magnet behaviour.
Three cationic [Ln4 ] squares (Ln=lanthanide) were isolated as single crystals and their structures solved as [Dy4 (μ4 -OH)(HL)(H2 L)3 (H2 O)4 ]Cl2 ⋅(CH3 OH)4 ⋅(H2 O)8 (1), [Tb4 (μ4 -OH)(HL)(H2 L)3 (MeOH)4 ]Cl2 ⋅(CH3 OH)4 ⋅(H2 O)4 (2) and [Gd4 (μ4 -OH)(HL)(H2 L)3 (H2 O)2 (MeOH)2 ]Br2 ⋅(CH3 OH)4 ⋅(H2 O)3 (3). The structures are described as hydroxo-centered squares of lanthanide ions, with each edge of the square bridged by a doubly deprotonated H2 L(2-) ligand. Alternating current magnetic susceptibility measurements show frequency-dependent out-of-phase signals with two different thermally assisted relaxation processes for 1, whereas no maxima in χM " appears above 2.0 K for complex 2. For 1, the estimated effective energy barrier for these two relaxation processes is 29 and 100 K. Detailed ab initio studies reveal that complex 1 possesses a toroidal magnetic moment. The ab initio calculated anisotropies of the metal ions in complex 1 were employed to simulate the magnetic susceptibility by using the Lines model (POLY_ANISO) and this procedure yields J1 =+0.01 and J2 =-0.01 cm(-1) for 1 as the two distinct exchange interactions between the Dy(III) ions. Similar parameters are also obtained for complex 1 (and 2) from specific heat measurements. A very weak antiferromagnetic super-exchange interaction (J1 =-0.043 cm(-1) and g=1.99) is observed between the metal centers in 3. The magnetocaloric effect (MCE) was estimated by using field-dependent magnetization and temperature-dependent heat-capacity measurements. An excellent agreement is found for the -ΔSm values extracted from these two measurements for all three complexes. As expected, 3 shows the largest -ΔSm variation (23 J Kg(-1) K(-1) ) among the three complexes. The negligible magnetic anisotropy of Gd indeed ensures near degeneracy in the (2S+1) ground state microstates, and the weak super-exchange interaction facilitates dense population of low-lying excited states, all of which are likely to contribute to the MCE, making complex 3 an attractive candidate for cryogenic refrigeration.
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