Reactivity of Thiolate and Hydrosulfide with a Mononuclear {FeNO} Complex Featuring a Very High N-O Stretching Frequency.

Synthesis, characterization, electronic structure, and redox reactions of a mononuclear {FeNO} complex with a very high N-O stretching frequency in solution are presented. Nitrosylation of [(L)Fe(DMF)] () (L = tris((1-methyl-4,5-diphenyl-1H-imidazol-2-yl)methyl)amine) produced a five-coordinate {FeNO} complex, [(L)Fe(NO)] (). While complex could accommodate an additional water molecule to generate a six-coordinate {FeNO} complex, [(L)Fe(NO)(HO)] (), the coordinated HO in dissociates to generate in solution.

Role of Labile Methanol on the Bio-inspired Catalytic Activity of a Zn(II)-based Compound: An Experimental and Theoretical Investigation.

Two Zn(II)-based compounds, [Zn L (OAc) (MeOH)] (1) and [Zn L (OAc) ] (2), have been reported where HL is (E)-4-bromo-2-methoxy-6-(((2-morpholino ethyl)imino) methyl)phenol and HL is (E)-4-bromo-2-methoxy-6-(((2-(piperazine-1-yle)ethyl)imino)methyl) phenol. Single-crystal X-ray diffraction (SCXRD) analysis unveils vivid change in structural arrangements and dimensionality from 1 to 2 due to change in coordinated atom from oxygen to nitrogen of the ligands. SCXRD study shows that compound 1 is dinuclear but compound 2 has a 1-dimensional polymeric structure having helical chain.

Synergistic Experimental and Theoretical Studies of Luminescent-Magnetic LnZn Clusters.

The present work is part of our ongoing quest for developing functional inorganic complexes using unorthodox pyridyl-pyrazolyl-based ligands. Accordingly, we report herein the synthesis, characterization, and luminescence and magnetic properties of four 3d-4f mixed-metal complexes with a general core of LnZn (Ln = Dy, Gd, Tb, and Eu). In stark contrast to the popular wisdom of using a compartmental ligand with separate islands of and coordinating sites for selective coordination, we have vindicated our approach of using a ligand with overcrowded N-coordinating sites that show equal efficiency with both 4f and 3d metals toward multinuclear cage-cluster formation.

A Nd6 molecular butterfly: a unique all-in-one material for SMM, MCE and maiden photosensitized opto-electronic device fabrication.

Besides iron, ironically neodymium (Nd) is the most ubiquitously used metal for magnetic purposes, even among the lanthanides, when it comes to the field of molecular magnetism, yet it ranks among the least studied metals. However, strong apathy towards this magnetic lanthanide means that vital information will be missed, which is required for the advancement of the subject. Herein, we have successfully demonstrated the usefulness of a hexanuclear neodymium complex as a magnetic material, and also in electronic device fabrication.

Sodium-Stuffed Open-Framework Quaternary Chalcogenide Built with (CuGaS) Ribbons Cross-Linked by Unusual Linear Cu(I) Pillars.

A quaternary compound, NaCuGaS, the first member in the A-Cu-Ga-S (A = alkali metal) series, has been synthesized from a solid-state metathesis reaction between NaGaS and CuCl as well as from a combination of NaS, Ga, Cu, and S. The compound crystallizes in a monoclinic crystal system, space group 2/, and represents a unique open-framework structure with channels filled with eight crystallographically distinct Na ions. The anionic framework is built up of infinite chains of corner-shared GaS tetrahedra fused together by an edge-shared dimer of CuS tetrahedra forming one-dimensional ribbons of (CuGaS), which are cross-linked by linearly coordinated S-Cu-S linkages resulting in a three-dimensional network with tunnels filled with Na atoms.

Ternary alkali ion thiogallates, AGaS (A = Li and Na), with isolated tetrahedral building units and their ionic conductivities.

Two new ternary thiogallates in the A5GaS4 (A = Li (i) and Na (ii)) series have been synthesized for the first time employing a gas passing route using oxide precursors and a high temperature solid state route using stoichiometric combinations of elements, respectively. Li5GaS4 crystallizes in the P21/m space group and the structure is built up of layers of corner sharing tetrahedra of LiS4 and GaS4 stacked along the a-axis and the octahedrally coordinated Li ions residing in the interlayer space. Na5GaS4 crystallizes in the Pbca space group and the structure consists of isolated (GaS4)5- tetrahedra held together by charge balancing sodium ions in distorted tetrahedral and octahedral coordination geometries.

Lanthanide clusters of phenanthroline containing a pyridine-pyrazole based ligand: magnetism and cell imaging.

In this contribution, we report the synthesis, characterization and luminescence-magnetic properties of Ln-clusters (Ln = Gd3+, Eu3+ and Tb3+) using a new pyridine-pyrazole functionalized ligand fitted with a chromophoric phenanthroline backbone. The unorthodox N-rich ligand forms isostructural trinuclear lanthanide complexes with a topology that closely resembles two interdigitating hairpins. The clusters crystallize in chiral space groups and also exhibit chirality for bulk samples, which were further confirmed using solid state CD spectra.

Naked Eye Cd Ion Detection and Reversible Iodine Uptake by a Three-Dimensional Pillared-Layered Zn-MOF.

A novel metal-organic framework (MOF), [Zn(tdca)(bppd)]·2DMF, has been synthesized solvothermally using the ligand thiophene-2,5-dicarboxylic acid (Htdca), coligand ,'-bis(4-pyridylmethylene)-1,4-benzenediamine (bppd), and Zn(NO). Single crystal X-ray crystallography reveals that the titled MOF is a three-dimensional pillared-layered MOF. A layer is constituted by a Zn(tdca) unit, and the layers are stabilized by the long hydrocarbon coligand, bppd, which acts as a pillar.

Structure and synthesis of copper-based Schiff base and reduced Schiff base complexes: a combined experimental and theoretical investigation of biomimetic catalytic activity.

Three copper(ii) complexes, [Cu(L1)(NCS)]n (1), [Cu(L1)(N3)]n (2) and [Cu(L2)(N3)] (3) were synthesized from one Schiff base ligand and one reduced Schiff base ligand, (E)-4-chloro-2-[(2-propylaminoethylimino)methyl]phenol (HL1) and 4-chloro-2-[(2-(propylaminoethylamino) methyl]phenol (HL2), respectively. All complexes were characterized by various physicochemical studies, such as FT-IR, UV-Vis, ESI-MS, EPR and single crystal X-ray diffraction. Complexes 1 and 2 have 1D polymeric chain-like structures bridging through thiocyanate and azide anions, whereas complex 3 has a mononuclear structure in the solid state.

Paradoxical design of a serendipitous pyrazolate bridging mode: a pragmatic strategy for inducing ineluctable ferromagnetic coupling.

In this contribution we have carried out a systematic magnetostructural investigation to establish a robust one-to-one correlation between the quasi-orthogonal bridging mode of a pyrazolate ring and ferromagnetic coupling. Generating a complex with an elusive quasi-orthogonal pyrazolate bridging is a challenging task but would ineluctably result in a ferromagnetic exchange pathway. Notwithstanding the rarity, we report herein a series of bis-pyrazolato copper complexes.

A free-standing, self-healing multi-stimuli responsive gel showing cryogenic magnetic cooling.

A novel Fe(iii)-based gel was synthesized via the self-assembly of Fe(iii) and pyridine 2,6 dicarboxylic acid. The synthesized gel has remarkable mechanical strength as well as self-sustainability. The metallogel also has thixotropic as well as self-healing properties.

Synthesis of MnO nanozymes from structurally characterized phenoxazinone synthase models based on manganese(iii) Schiff base complexes.

Three mononuclear and one hexanuclear manganese(iii) complexes, [Mn(L)(HO)]·Cl (1), [Mn(L)(HO)]·Br (2), [Mn(L)(HO)]·NO (3), and [Mn(L)(NCS)] (4), have been synthesized using a Schiff-base ligand, namely (E)-2-((3-(2-hydroxyethylamino)propylimino)methyl)phenol (HL), and structurally characterized by the usual physicochemical techniques such as UV-Vis, FT-IR, ESI-MS, EPR and single crystal XRD. The structure of complex 4 is unique among all four complexes as the sixth coordination position of manganese is fulfilled by the oxygen atom of a neighbouring unit by covalent interaction. The phenoxazinone synthase like activity of all four complexes has been thoroughly investigated using three different substrates, o-aminophenol (OAP), 2-amino-4-methylphenol (MAP) and 3-amino-4-hydroxybenzoic acid (CAP).

Correction to "Temperature-Induced Single-Crystal-to-Single-Crystal Transformations with Consequential Changes in the Magnetic Properties of Fe(III) Complexes".

[This corrects the article DOI: 10.1021/acsomega.8b03400.

Exploration of catecholase-like activity of a series of magnetically coupled transition metal complexes of Mn, Co and Ni: new insights into the solution state behavior of Mn complexes.

A series of tri-nuclear complexes of general formula [ML(OAc)], where M = Mn (1), Co (2) and Ni (3), (HL = (E)-4-bromo-2-(((2-morpholinoethyl)imino)methyl)phenol), have been synthesized. Single crystal X-ray crystallography reveals that each molecule contains three metal ions which are bridged by four acetate moieties. In the solution phase, the complexes are present as mononuclear species.

Temperature-Induced Single-Crystal-to-Single-Crystal Transformations with Consequential Changes in the Magnetic Properties of Fe(III) Complexes.

The present article deals with an one-to-one structure-property correspondence of a dinuclear iron complex, [Dipic(HO)FeOH]·HO () (Dipic = pyridine-2,6-dicarboxylic acid). Variable-temperature X-ray single-crystal structural analysis confirms a phase transition of complex to complex ([Dipic(HO)FeOH]) at 120 °C. Further, single-crystal-to-single-crystal (SCSC) transformation was monitored by temperature-dependent single crystal X-ray diffraction, powder X-ray diffraction, time-dependent Fourier-transform infrared spectroscopy, and differential scanning calorimetry.

Multifunctional Properties of a 1D Helical Co(II) Coordination Polymer: Toward Single-Ion Magnetic Behavior and Efficient Dye Degradation.

This contribution deals with the synthesis and utilization of a new pyrazole-based unsymmetrical ligand, 3-(3-carboxyphenyl)-1-pyrazole-5-carboxylic acid (HCPCA), for generating multifunctional materials. The reaction with the Co(II) salt in the presence of a co-ligand 2,9-dimethyl phenanthroline (dmphen) results in the formation of the helical compound {[Co(dmphen)(CPCA)]DMF} (). However, two isostructural monomeric complexes are formed {[M(HCPCA)(HO)], M = Co(II), () and Mn(II) ()} when reactions were carried out in the absence of dmphen.

Magnetically Frustrated Quaternary Chalcogenides with Interpenetrating Diamond Lattices.

A series of quaternary sulfides of the composition NaMGaS (M = Mn (1), Fe (2), and Co (3)) have been synthesized in sealed quartz ampules. In these compounds, divalent transition metal and Ga occupy the same crystallographic site in the Ga-S network, forming a supertetrahedral, T2 (adamantane) unit, through the corner-sharing of four M/GaS tetrahedra. The corner sulfur atoms of the T2 clusters are further connected to similar T2 units to form an open continuous three-dimensional (3D) anionic framework of composition {[GaMS]}.

Crystal structure of a chloride-bridged copper(II) dimer: piperazine-1,4-dium bis-(di-μ-chlorido-bis[(4-carboxypyridine-2-carboxyl-ato-κ,)chlorido-cuprate(II)].

Crystals of a new dimeric chloride-bridged cuprate(II) derived from pyridine-2,4-di-carb-oxy-lic acid were obtained solvothermally in the presence of piperazine and hydro-chloric acid. The crystal structure determination of the title salt, (CHN)[Cu(CHNO)Cl], revealed one of the carboxyl groups of the original pyridine-2,4-di-carb-oxy-lic acid ligand to be protonated, whereas the other is deprotonated and binds together with the pyridine N atom to the Cu atom. The coordination environment of the Cu atom is distorted square-pyramidal.

Synthesis, structure, magnetic and biological activity studies of bis-hydrazone derived Cu(ii) and Co(ii) coordination compounds.

Four coordination compounds of formulae [Cu(II)2(H2L(1))(HL(1))](ClO4)3·H2O (1), [Cu(II)2(H2L(2))(CH3OH)2](ClO4)2·2CH3OH (2), [Co(II)2(H2L(1))2](ClO4)4 (3) and [Co(II)2(H2L(2))2]·2H2O (4) were synthesized via self-assembly of succinohydrazone derived ligands (H2L(1) = N',N'-4-bis(2-pyridyl)succinohydrazide, H4L(2) = N',N'-4-bis(2-hydroxybenzylidene)succinohydrazide) and Cu(2+) and Co(2+) ions, respectively. The compounds were characterized by crystal structure determination, magnetic measurements and biological activities. Compounds 1, 3 and 4 have discrete double helicate structures, whereas compound 2 is a one-dimensional chain.

Metallic Ternary Telluride with Sphalerite Superstructure.

A new ternary compound with composition Cu5Sn2Te7 has been synthesized using the stoichiometric reaction of Cu, Sn, and Te. The compound crystallizes in C2 space group with unit cell parameters of a = 13.549(2) Å, b = 6.

A family of Fe(3+) based double-stranded helicates showing a magnetocaloric effect, and Rhodamine B dye and DNA binding activities.

Herein, the synthesis, structural characterization, magnetic properties and guest binding activities of four Fe(3+) based double-stranded helicates namely; [Fe2(L)2](ClO4)(Cl)·4(CH3OH)·2(H2O) (), [Fe2(L)2](BF4)2·2(H2O) (), [Fe2(L)2](NO3)2·3(CH3OH)·2(H2O) (), and [Fe2(L)2](Cl)2·2(CH3OH)·4(H2O) () are reported. Complexes have been synthesized using the hydrazide-based ligand H2L (H2L = N'1,N'4-bis(2-hydroxybenzylidene)succinohydrazide) and the corresponding Fe(2+) salts. Each of the independent cationic complexes [Fe2(L)2](2+) shows double-stranded helicates from the self-assembly of the ligand and metal ions in a 2 : 2 ratio, where the individual Fe(3+) centre is lying on a C2-axis and the ligand strands wrap around it.

Synthesis, crystal structure and study of magnetocaloric effect and single molecular magnetic behaviour in discrete lanthanide complexes.

The synthesis, crystal structure and magnetic properties of four polynuclear lanthanide coordination complexes having molecular formulae, [Gd3(2)(1)L(H2O)8(Cl)](Cl)4·10H2O (1), [Dy3L(2)(1)(H2O)9](Cl)5·6H2O (2) [Gd6L(2)(2)(HCO2)4(μ3-OH)4(DMF)6(H2O)2](Cl)2·4H2O (3) and [Dy6L(2)(2)(HCO2)4(μ3-OH)4(DMF)6(H2O)2](Cl)2·4H2O (4) (where H2L(1) = bis[(2-pyridyl)methylene]pyridine-2,6-dicarbohydrazide and H4L(2) = bis[2-hydroxy-benzylidene]pyridine-2,6-dicarbohydrazide) are reported. Structural investigation by X-ray crystallography reveals similar structural features for complexes 1 and 2 and they exhibit butterfly like shapes of the molecules. Non-covalent interactions between the molecules create double helical arrangements for both molecules.

Two isostructural 3D lanthanide coordination networks (Ln = Gd(3+), Dy(3+)) with squashed cuboid-type nanoscopic cages showing significant cryogenic magnetic refrigeration and slow magnetic relaxation.

Two isostructural lanthanide-based 3D coordination networks [Ln = Gd(3+) (1), Dy(3+)(2)] with densely packed distorted cuboid nanoscopic cages are reported for the first time. Magnetic characterization reveals that complex 1 shows a significant cryogenic magnetocaloric effect (-ΔSm = 44 J kg(-1) K(-1)), whereas 2 shows slow relaxation of magnetization.

Synthesis and characterization of two discrete Ln₁₀ nanoscopic ladder-type cages: magnetic studies reveal a significant cryogenic magnetocaloric effect and slow magnetic relaxation.

Two unique lanthanide-based cages [Ln10(L)5(μ2-OH)6(H2O)22](Cl)4⋅7 H2O ([Gd10] and [Dy10]) have been synthesized by using a hydrazone-based ligand H4L (H4L=2,6-bis[(3-methoxysalicylidene)hydrazinecarbonyl]pyridine) and LnCl3⋅x H2O. Structural characterization of [Gd10] reveals an aesthetically pleasing self-assembly of five L(4-) and ten Gd(3+) ions forming a 2×[1×5] rectangular array. The ladder-shaped cage consists of three "rungs" and two "rails" that are occupied by five ligands.

New onset paediatric epilepsy in 1-5 years age group children--approach to management in a tertiary care centre with newer anti-epileptic levetiracetam.

Epilepsy is a common paediatric neurologic disorder that is difficult to manage in a substantial portion of children, highlighting the continued need for more effective and better tolerated drugs. A multicentric study was conducted from August, 2011 to July, 2013 using levetiracetam (LEV) in newely diagnosed epilepsy in 122 young children of 1-5 years age group to find its role in practical scenario depending upon the knowledge from prior literature available. It has been demonstrated effective as adjunctive therapy as well as monotherapy for new-onset partial seizures and generalised tonic-clonic seizures (GTCS) but it acts better as adjunctive therapy than the monotherapy.