Coordination self-assembly of tetranuclear Pt(II) macrocycles with an organometallic backbone for sensing of acyclic dicarboxylic acids

Coordination self-assembly of a series of tetranuclear Pt(II) macrocycles containing an organometallic backbone incorporating ethynyl functionality is presented. The 1 : 1 combination of a linear acceptor 1,4-bistrans-Pt(PEt3)(2)(NO3)(ethynyl)]benzene (1) with three different dipyridyl donor `clips' (L-a-L-c) afforded three 2 + 2] self-assembled Pt-4(II) macrocycles (2a-2c) in quantitative yields, respectively L-a = 1,3-bis-(3-pyridyl)isothalamide; L-b = 1,3-bis(3-pyridyl)ethynylbenzene; L-c = 1,8-bis(4-pyridyl)ethynylanthracene]. These macrocycles were characterized by multinuclear NMR (H-1 and P-31); ESI-MS spectroscopy and the molecular structures of 2a and 2b were established by single crystal X-ray diffraction analysis. These macrocycles (2a-2c) are fluorescent in nature. The amide functionalized macrocycle 2a is used as a receptor to check the binding affinity of aliphatic acyclic dicarboxylic acids. Such binding affinity is examined using fluorescence and UV-Vis spectroscopic methods. A solution state fluorescence study showed that macrocycle 2a selectively binds (K-SV = 1.4 x 10(4) M-1) maleic acid by subsequent enhancement in emission intensity. Other aliphatic dicarboxylic acids such as fumaric, succinic, adipic, mesaconic and itaconic acids caused no change in the emission spectra; thereby demonstrating its potential use as a macrocyclic receptor in distinction of maleic acid from other aliphatic dicarboxylic acids.

Exploring the color of transition metal ions in irregular coordination geometries: new colored inorganic oxides based on the spiroffite structure, Zn2-xMxTe3O8 (M = Co, Ni, Cu)

We describe the synthesis, crystal structures, and optical absorption spectra of transition metal substituted spiroffite derivatives, Zn2-xMxTe3O8 (M-II = Co, Ni, Cu; 0 < x <= 1.0). The oxides are readily synthesized by solid state reaction of stoichiometric mixtures of the constituent binaries at 620 degrees C. Reitveld refinement of the crystal structures from powder X-ray diffraction (XRD) data shows that the Zn/MO6 octahedra are strongly distorted, as in the parent Zn2Te3O8 structure, consisting of five relatively short Zn/M-II-O bonds (1.898-2.236 angstrom) and one longer Zn/M-II-O bond (2.356-2.519 angstrom). We have interpreted the unique colors and the optical absorption/diffuse reflectance spectra of Zn2-xMxTe3O8 in the visible, in terms of the observed/irregular coordination geometry of the Zn/M-II-O chromophores. We could not however prepare the fully substituted M2Te3O8 (M-II = Co, Ni, Cu) by the direct solid state reaction method. Density Functional Theory (DFT) modeling of the electronic structure of both the parent and the transition metal substituted derivatives provides new insights into the bonding and the role of transition metals toward the origin of color in these materials. We believe that transition metal substituted spiroffites Zn2-xMxTe3O8 reported here suggest new directions for the development of colored inorganic materials/pigments featuring irregular/distorted oxygen coordination polyhedra around transition metal ions.

A new 3D cadmium(II) coordination polymer having mu(4)-oxalato, mu-aquo and mu-chlorido bridges: crystal structure, solid state fluorescence and thermal behavior

A new 3D cadmium(II) coordination polymer, Cd(C2O4)(0.5)Cl(H2O)](n) (1) has been synthesized from a mixture of CdCl2. H2O and (NH4)(2)C2O4 in a slightly acidic pH. Its molecular structure was determined by single crystal X-ray diffraction which reveals that the new polymeric structure consists of simultaneous mu(4)-oxalato, mu-aquo, and mu-chlorido bridges between the metal centers, embedded in distorted pentagonal bipyramidal geometries. On thermal analysis compound exhibits high thermal stability up to 330 degrees C. Compound 1 also exhibits strong fluorescent emission. (c) 2013 Elsevier B.V. All rights reserved.

Solvent-templated supramolecular isomerism in 2D coordination polymer constructed by (Ni2CoII)-Co-II nodes and dicyanamido spacers: drastic change in magnetic behaviours

Two heterometallic coordination polymers (CPs) have been prepared using (NiL)-L-II](2)Co-II (where H2L = N,N'-bis(salicylidene)-1,3-propanediamine) as nodes and dicyanamido spacers by varying the solvent for synthesis. Structural characterizations revealed that methanol assisted the formation of a two-dimensional (4,4) connected rhombic grid network of (NiL)(2)Co(NCNCN)2](infinity) (1a) whereas relatively less polar acetonitrile afforded a different superstructure {(NiL)(2)Co(NCNCN)(2)]center dot CH3CN}(infinity) (1b) with a two-dimensional (4,4) connected square grid network. The presence of acetonitrile molecules in the structure of 1b seems to change the spatial orientation of the terminal metalloligands NiL] from pseudo-eclipsed in 1a to staggered-like in 1b around the central Co(II). These structural changes in the nodes together with the conformationally flexible dicyanamido spacers, which are cis coordinated to the Co(II) in both trinuclear units, led to the differences in the final 2D network. Variable-temperature magnetic susceptibility measurements revealed that this supramolecular isomerism led to a drastic transition from spin-frustrated antiferromagnetism for 1a to a dominant ferromagnetic behaviour for 1b. The geometrical differences in Ni2Co coordination clusters (CCs) which are scalene triangular in 1a but nearly linear in 1b, are held responsible for the changes of the magnetic properties. The DFT calculations of exchange interactions between metal centres provide a clear evidence of the role played by the fundamental geometrical factors on the nature and magnitude of the magnetic coupling in these pseudo-polymorphic CPs.

Sr2+ and Cd2+ coordination polymers: the effect of the different coordinating behaviour of a newly designed tricarboxylic acid

This article presents the investigation of the coordination behavior of a newly synthesized tricarboxylate ligand, obtained by joining imidazole dicarboxylic acid and 4-carboxybenzyl moieties cbimdaH(3), 1-(4-carboxybenzyl)-1H-imidazole-4,5-dicarboxylic acid]. Two novel coordination polymers were obtained through solvothermal reactions under similar conditions namely Sr(cbimdaH)(H2O)](n) (1) and Cd-2(cbimdaH)(2)(H2O)(6)](n)center dot(DMF)(3n)(H2O)(3n) (2), with the ligand behaving as a dianionic tricarboxylate linker. The single crystal X-ray structures show that while 1 forms a 3D coordination polymer, 2 forms a 1D polymer which is further assembled in three dimensions through supramolecular interactions (H-bonding). Complex 1 consists of Sr2+ ions in a distorted dodecahedral coordination geometry, while 2 consists of Cd2+ ions in distorted pentagonal bipyramidal geometries. A topology study reveals that 1 has a new topology based on the 5,6-coordinated 3D net architecture. The luminescence properties of the complexes in the solid state and their thermal stabilities were studied.

Template-free multicomponent coordination-driven self-assembly of Pd(II)/Pt(II) molecular cages

Recent years have seen a tremendous increase in the interest for constructing hollowed-out molecular frameworks, for their potential uses. Metal-ligand coordination-driven self-assembly has provided multitudes of opportunities in the formation of molecular architectures of desired shapes and sizes, with the help of the information already coded in the components. This article summarizes the recent developments in the construction of multicomponent molecular cages through this process, with a focus on the decreasing relevance of templates, and use of these systems in catalysis/host-guest chemistry.

Coordination of Reactive Power in Grid-Connected Wind Farms for Voltage Stability Enhancement

This paper studies the feasibility of utilizing the reactive power of grid-connected variable-speed wind generators to enhance the steady-state voltage stability margin of the system. Allowing wind generators to work at maximum reactive power limit may cause the system to operate near the steady-state stability limit, which is undesirable. This necessitates proper coordination of reactive power output of wind generators with other reactive power controllers in the grid. This paper presents a trust region framework for coordinating reactive output of wind generators-with other reactive sources for voltage stability enhancement. Case studies on 418-bus equivalent system of Indian southern grid indicates the effectiveness of proposed methodology in enhancing the steady-state voltage stability margin.

Salmonella methylglyoxal detoxification by STM3117-encoded lactoylglutathione lyase affects virulence in coordination with Salmonella pathogenicity island 2 and phagosomal acidification

Intracellular pathogens such as Salmonella enterica serovar Typhimurium (S. Typhimurium) manipulate their host cells through the interplay of various virulence factors. A multitude of such virulence factors are encoded on the genome of S. Typhimurium and are usually organized in pathogenicity islands. The virulence-associated genomic stretch of STM3117-3120 has structural features of pathogenicity islands and is present exclusively in non-typhoidal serovars of Salmonella. It encodes metabolic enzymes predicted to be involved in methylglyoxal metabolism. STM3117-encoded lactoylglutathione lyase significantly impacts the proliferation of intracellular Salmonella. The deletion mutant of STM3117 (Delta lgl) fails to grow in epithelial cells but hyper-replicates in macrophages. This difference in proliferation outcome was the consequence of failure to detoxify methylglyoxal by Delta lgl, which was also reflected in the form of oxidative DNA damage and upregulation of kefB in the mutant. Within macrophages, the toxicity of methylglyoxal adducts elicits the potassium efflux channel (KefB) in the mutant which subsequently modulates the acidification of mutant-containing vacuoles (MCVs). The perturbation in the pH of the MCV milieu and bacterial cytosol enhances the Salmonella pathogenicity island 2 translocation in Delta lgl, increasing its net growth within macrophages. In epithelial cells, however, the maturation of Delta lgl-containing vacuoles were affected as these non-phagocytic cells maintain less acidic vacuoles compared to those in macrophages. Remarkably, ectopic expression of Toll-like receptors 2 and 4 on epithelial cells partially restored the survival of Delta lgl. This study identified a novel metabolic enzyme in S. Typhimurium whose activity during intracellular infection within a given host cell type differentially affected the virulence of the bacteria.

A common stochastic accumulator with effector-dependent noise can explain eye-hand coordination

The computational architecture that enables the flexible coupling between otherwise independent eye and hand effector systems is not understood. By using a drift diffusion framework, in which variability of the reaction time (RT) distribution scales with mean RT, we tested the ability of a common stochastic accumulator to explain eye-hand coordination. Using a combination of behavior, computational modeling and electromyography, we show how a single stochastic accumulator to threshold, followed by noisy effector-dependent delays, explains eye-hand RT distributions and their correlation, while an alternate independent, interactive eye and hand accumulator model does not. Interestingly, the common accumulator model did not explain the RT distributions of the same subjects when they made eye and hand movements in isolation. Taken together, these data suggest that a dedicated circuit underlies coordinated eye-hand planning.

A Pd-24 Pregnant Molecular Nanoball: Self-Templated Stellation by Precise Mapping of Coordination Sites

We found that Pd(II) ion (M) and the smallest 120 bidentate donor pyrimidine (L-a) self-assemble into a mononuclear M(L-a)(4) complex (1a) instead of the expected smallest M-12(L-a)(24) molecular ball (1), presumably due to the weak coordination nature of the pyrimidine. To construct such a pyrimidine bridged nanoball, we employed a new donor tris(4-(pyrimidin-5-yl)phenyl)amine (L); which upon selective complexation with Pd(II) ions resulted in the formation of a pregnant M24L24 molecular nanoball (2) consisting of a pyrimidine-bridged Pd-12 baby-ball supported by a Pd-12 larger mother-ball. The formation of the baby-ball was not successful without the support of the mother-ball. Thus, we created an example of a self-assembly where the inner baby-ball resembling to the predicted M-12(L-a)(24) ball (1) was incarcerated by the giant outer mother-ball by means of geometrical constraints. Facile conversion of the pregnant ball 2 to a smaller M-12(L-b)(24) ball 3 with dipyridyl donor was achieved in a single step.

High aspect ratio, processable coordination polymer gel nanotubes based on an AIE-active LMWG with tunable emission

A new TPE based low molecular weight gelator (LMWG) which displays both AIE and MCIE phenomena in gel state has been synthesized. LMWG self-assembles to form 1D nanofibers which undergo morphology transformation to coordination polymer gel (CPG) nanotubes upon metal ion coordination. CPG shows enhanced mechanical stability along with tunable emission properties.

Structural diversities in Cu(I) and Ag(I) sulfonate coordination polymers and their anion exchange properties

Two new Cu(I) compounds, namely Cu-2(bds)(bpy)(2)]center dot 2H(2)O (1) and Cu-4(bds)(2)(azpy)(4)]center dot 6H(2)O (3) (where bds = benzene-1,3-disulfonate, bpy = 4,4'-bipyridine and azpy = 4,4'-azopyridine), and four Ag(I) compounds, namely Ag-2(bds)(bpy)(2)]center dot 2H(2)O (2), Ag-2(bds)(azpy)(2)]center dot 4H(2)O (4), Ag(bds)(1/2)(bpe)]center dot 3H(2)O (5), and Ag-4(bds)(2)(tmdp)(4)]center dot 9H(2)O (6) (where bpe = 1,2-di(4-pyridyl) ethylene and tmdp = 4,4'trimethylenedipyridine), have been synthesized, and their structures were determined and characterized by elemental analysis, IR, UV-vis and thermal studies. The structure of the compounds changed from 1D (1 and 2) to 2D (3-5) and interpenetrated 3D (6). In the case of 5, a solid-state 2 + 2] photochemical cycloaddition reaction has been performed. Compound 2 exhibits a reversible anion exchange for perchlorate and permanganate, whereas the other compounds (1, 3-6) exhibit an irreversible anion exchange behaviour for perchlorate. Catalytic studies on 2 indicate Lewis acidity.

Eye-hand coordination during a double-step task: evidence for a common stochastic accumulator

Many studies of reaching and pointing have shown significant spatial and temporal correlations between eye and hand movements. Nevertheless, it remains unclear whether these correlations are incidental, arising from common inputs (independent model); whether these correlations represent an interaction between otherwise independent eye and hand systems (interactive model); or whether these correlations arise from a single dedicated eye-hand system (common command model). Subjects were instructed to redirect gaze and pointing movements in a double-step task in an attempt to decouple eye-hand movements and causally distinguish between the three architectures. We used a drift-diffusion framework in the context of a race model, which has been previously used to explain redirect behavior for eye and hand movements separately, to predict the pattern of eye-hand decoupling. We found that the common command architecture could best explain the observed frequency of different eye and hand response patterns to the target step. A common stochastic accumulator for eye-hand coordination also predicts comparable variances, despite significant difference in the means of the eye and hand reaction time (RT) distributions, which we tested. Consistent with this prediction, we observed that the variances of the eye and hand RTs were similar, despite much larger hand RTs (similar to 90 ms). Moreover, changes in mean eye RTs, which also increased eye RT variance, produced a similar increase in mean and variance of the associated hand RT. Taken together, these data suggest that a dedicated circuit underlies coordinated eye-hand planning.

Conformation-selective coordination-driven self-assembly of a ditopic donor with Pd-II acceptors

Coordination-driven self-assembly of 3-(5-(pyridin-3-yl)-1H-1,2,4-triazol-3-yl)pyridine (L) was investigated with 90 degrees cis-blocked Pd(II) acceptors and tetratopic Pd(NO3)(2). Although the ligand is capable of binding in several different conformations (acting as a ditopic donor through the pyridyl nitrogens), the experimental results (including X-ray structures) showed that it adopts a particular conformation when it binds with 90 degrees cis-blocked Pd(II) acceptors (two available sites) to yield 2 + 2] self-assembled macrocycles. On the other hand, with Pd(NO3)(2) (where four available sites are present) a different conformer of the same donor was selectively bound to form a molecular cubic cage. The experimental findings were corroborated well with the density functional theory (B3LYP) calculations. The tetratopic Pd(NO3)(2) yielded a 6 + 12] self-assembled Pd6L12 molecular cube, which contains a potential void occupied by nitrate and perchlorate ions. Being a triazole based ligand, the free space inside the cage is enriched with several sp(2) hybridised nitrogen atoms with lone pairs of electrons to act as Lewis basic sites. Knoevenagel condensation reactions of several aromatic aldehydes with active methylene compounds were successfully performed in reasonably high yields in the presence of the cage.

Template-free coordination-driven self-assembly of discrete hexanuclear prismatic cages employing half-sandwich octahedral Ru-2(II) acceptors and triimidazole donors

Coordination-driven self-assembly of dinuclear half-sandwich p-cymene ruthenium(II) complexes Ru-2(mu-eta(4)-C2O4)(CH3OH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1a) and Ru-2(mu-eta(4)-C6H2O4)(CH3OH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1b) separately with imidazole-based tritopic donors (L-1-L-2) in methanol yielded a series of hexanuclear 3+2] trigonal prismatic cages (2-5), respectively L-1 = 1,3,5-tris(imidazole-1-yl) benzene; L-2 = 4,4',4 `'-tris(imidazole-1-yl) triphenylamine]. All the self-assembled cages 2-5 were characterized by various spectroscopic techniques (multinuclear NMR, Infra-red and ESI-MS) and their sizes, shapes were obtained through geometry optimization using molecular mechanics universal force field (MMUFF) computation. Despite the possibility due to the free rotation of donor sites of imidazole ligands, of two different atropoisomeric prismatic cages (C-3h or C-s) and polymeric product, the self-selection of single (C(3)h) conformational isomeric cages as the only product is a noteworthy observation. (C) 2015 Elsevier B.V. All rights reserved.