Segregated self-assembly and pillaring action of aliphatic dicarboxylic acids in the super structure of Cu-picolinate complexes

Three new supramolecular assemblies of co-crystallized metal complexes and aliphatic dicarboxylic acids, {[Cu(pic)(2)(H2O)(2)](H(2)mal)}(n) (1), {[Cu(pic)(2)(H2O)(2)](H(2)mal)(2)(H2O)(2)}(n) (2) and {[Cu(pic)(2)(MeOH)](H(2)succ)}(n) (3) {Hpic = 2-picolinic acid, H(2)mal = malonic acid and H(2)succ = succinic acid} have been synthesized and characterized by X-ray single-crystal structure determination. The crystal packings of the complexes reveal that supramolecular associations of the monomeric complex units lead to the formation of layers through hydrogen bonding. In all the complexes, the dicarboxylic acid units connect the 2-D layers to act as pillars. The interaction between water molecules and the dicarboxylic acid plays an important role in the overall supramolecular assembly. (C) 2008 Elsevier Ltd. All rights reserved.

4,4 '-Dipyridyl-N,N '-dioxide complexes of metal-thiocyanate/selenocyanate: pi-stacked molecular rods as three-dimensional support for two-dimensional polymeric sheets and intra/interchain S center dot center dot center dot S interaction dependent architecture of the R-2(2)(8) synthon driven assembly of one-dimensional polymeric chains

Three supramolecular complexes of Co(II) using SCN-/SeCN- in combination with 4,4'-dipyridyl-N,N'-dioxide (dpyo), i.e., {[Co(SCN)(2)(dpyo)(2)].(dpyo)}(n) ( 1), {[Co(SCN)(2)(dpyo)(H2O)(2)].(H2O)}(n) ( 2), {[Co(SeCN)(2)(dpyo)(H2O)(2)]center dot(H2O)}(n) ( 3), have been synthesized and characterized by single-crystal X-ray analysis. Complex 1 is a rare example of a dpyo bridged two-dimensional (2D) coordination polymer, and pi-stacked dpyo supramolecular rods are generated by the lattice dpyo, passing through the rhombic grid of stacked layers, resulting in a three-dimensional (3D) superstructure. Complexes 2 and 3 are isomorphous one-dimensional (1D) coordination polymers [-Co-dpyo-Co-] that undergo self-assembly leading to a bilayer architecture derived through an R-2(2)(8) H-bonding synthon between coordinated water and dpyo oxygen. A reinvestigation of coordination polymers [Mn(SCN)(2)(dpyo)( H2O)(MeOH)](n) ( 4) and {[Fe(SCN)(2)(dpyo)(H2O)(2)]center dot(H2O)}(n) ( 5) reported recently by our group [ Manna et al. Indian J. Chem. 2006, 45A, 1813] reveals brick wall topology rather than bilayer architecture is due to the decisive role of S center dot center dot center dot S/Se center dot center dot center dot Se interactions in determining the helical nature in 4 and 5 as compared to zigzag polymeric chains in 2 and 3, although the same R-2(2)(8) synthon is responsible for supramolecular assembly in these complexes.

Polymorphism in [Co(SCN)(4)(ppz-H)(2)] (ppz, piperazine)

A one-pot reaction of [Co(NO3)(2)center dot 6H(2)O and piperazine] with NH4SCN/NaSCN in water-methanol (1:1) solvent leads to two polymorphs of [Co(SCN)(4)(ppz-H)(2)] (ppz, piperazine) (I and II). X-ray crystal structure reveals both have same space group but the differences in the alignment of pendant SCN- leads to two polymorphs. In I, trifurcated N-H...S hydrogen bonding plays a prominent role in crystal packing leading to S...S interactions between SCN fragments but in II, no such trifurcation arises and thereby the crystal packing occurs through hydrogen bonding interactions only leading to a distinctly different network topology. TG/DSC and FT-IR study reveal they are enantiotropically related. (c) 2007 Elsevier Ltd. All rights reserved.

2D parallel interpenetration of [M-2(bpp)(4)X-4] [M, Fe(II)/Co(II); bpp, 4,4 '-trimethylenedipyridine; X, SCN-SeCN- and N-3(-)] complexes: pseudohalide-dependent conformation of bpp

Three coordination complexes of Co(II)/Fe(II) with 4,4'-trimethylenedipyridine (bpp) and pseudohalides (SCN-, SeCN- and N-3(-)) have been synthesized. The complexes have been characterized by X-ray single crystal structure determination. They are isomorphous having 2D layers in which two independent wavy nets display parallel interwoven structures. Pseudohalide binds metal centers through N terminal and occupies the trans axial positions of the octahedral metal coordination environment. Pseudohalide remains pendant on both sides of the polymeric layer and help the stacking through hydrogen bonding. The conformation of bpp in the interpenetrated nets is observed to be dependent on the choice of pseudohalide. (C) 2008 Elsevier Inc. All rights reserved.

Concomitant polymorphism of an antiferromagnetically coupled dicopper(II,II) complex with single strand helical assembly: synthesis, structure, DSC, magnetic and heterogeneous catalytic studies

Two concomitant polymorphic coordination complexes (dark blue - I and black - II) with the formula (Cu2C44H60N4O4) have been synthesized and characterized crystallographically. Magnetic measurements show the presence of a strong antiferromagnetic interaction and the 2J value corresponds extremely well to the theoretically calculated one, indicating the fact that it follows nicely the magneto-structural relationship. Immobilization of the copper(II) complex I on a 2D-hexagonal mesoporous silica showed good catalytic efficiency in the liquid phase partial oxidation of olefins in the presence of TBHP as an oxidant. (C) 2009 Elsevier Ltd. All rights reserved.

Geometrical isomers of [TEAH][Co(L-Se)(2)]center dot xH(2)O: synthesis, structural, spectroscopic and computational studies

Trans-1, [HNEt3][Co-III(L-Se)(2)]center dot H2O and cis-1, [HNEt3][Co-III(L-Se)(2)]center dot 3H(2)O have been synthesized and characterized by single-crystal X-ray studies. The counter ion Et3NH+ plays a crucial role in the crystal packing leading to the formation of two distinctly different supramolecular assemblies in the two complexes. In trans-1, Co-bisphenolate units and triethylamine molecules are arranged in a linear fashion leading to a supramolecular columnar assembly along the crystallographic a-axis. In this assembly, triethylammonium ions are sandwiched between successive Co-bisphenolate units and act as gluing agents joining Co-bisphenolate units on either side through C-H center dot center dot center dot pi interactions. In sharp contrast to trans-1, Co-bisphenolate units and triethylammonium ions in cis-1 are arranged in a helical supramolecular assembly through similar C-H center dot center dot center dot pi interactions along the crystallographic b-axis. The Se center dot center dot center dot Se van der Waals interactions may be responsible for the predominant occurrence of the cis-isomer. The cyclic voltammetric studies showed quasi-reversible waves for the cobalt(III) -> cobalt(II) reductions with E-1/2 = 0.635 and 0.628 V vs. Ag/AgCl for cis-1 (at similar to 5 degrees C) and trans-1 (at similar to 25 degrees C), respectively. DFT calculations show that the trans-form is the thermodynamic product with higher stability than the cis-one, which is consistent with the variable temperature H-1 NMR studies

Transport impacts on atmosphere and climate: shipping

Emissions of exhaust gases and particles from oceangoing ships are a significant and growing contributor to the total emissions from the transportation sector. We present an assessment of the contribution of gaseous and particulate emissions from oceangoing shipping to anthropogenic emissions and air quality. We also assess the degradation in human health and climate change created by these emissions. Regulating ship emissions requires comprehensive knowledge of current fuel consumption and emissions, understanding of their impact on atmospheric composition and climate, and projections of potential future evolutions and mitigation options. Nearly 70% of ship emissions occur within 400 km of coastlines, causing air quality problems through the formation of ground-level ozone, sulphur emissions and particulate matter in coastal areas and harbours with heavy traffic. Furthermore, ozone and aerosol precursor emissions as well as their derivative species from ships may be transported in the atmosphere over several hundreds of kilometres, and thus contribute to air quality problems further inland, even though they are emitted at sea. In addition, ship emissions impact climate. Recent studies indicate that the cooling due to altered clouds far outweighs the warming effects from greenhouse gases such as carbon dioxide (CO2) or ozone from shipping, overall causing a negative present-day radiative forcing (RF). Current efforts to reduce sulphur and other pollutants from shipping may modify this. However, given the short residence time of sulphate compared to CO2, the climate response from sulphate is of the order decades while that of CO2 is centuries. The climatic trade-off between positive and negative radiative forcing is still a topic of scientific research, but from what is currently known, a simple cancellation of global mean forcing components is potentially inappropriate and a more comprehensive assessment metric is required. The CO2 equivalent emissions using the global temperature change potential (GTP) metric indicate that after 50 years the net global mean effect of current emissions is close to zero through cancellation of warming by CO2 and cooling by sulphate and nitrogen oxides.

Output sustainability to exogenous and endogenous shocks: evidence from emerging economies

This paper studies the impact of exogenous and endogenous shocks (exogenous shock is used interchangeably with external shock; endogenous shock is used interchangeably with domestic shock) on output fluctuations in post-communist countries during the 2000s. The first part presents the analytical framework and formulates a research hypothesis. The second part presents vector autoregressive estimation and analysis model proposed by Pesaran (2004) and Pesaran and Smith (2006) that relates bank real lending, the cyclical component of output and spreads and accounts for cross-sectional dependence (CD) across the countries. Impulse response functions show that exogenous positive shock lead to a drop in output sustainability for 9 over 12 Central Eastern European countries and Russia, when the endogenous shock is mild and ambiguous. Moreover, the effect of exogenous shock is more significant during the crises. Variance decompositions show that exogenous shock in the aftermath of crisis had a substantial impact on economic activity of emerging economies.

Contribution to The World Goes Pop exhibition catalogue

Biographies for artists Barel, Joav (p.174), Brudascu, Cornel (p.177), Bucan, Boris (p.178), Chicago, Judy (p.182), Ivekovic, Sanja (p.197), Komar and Melamid (p.200), Lach-Lachowicz, Natalia (p.203), Otasevic, Dusan (p.212), Overstreet, Joe (p.214), Pininska - Beres, Maria (p.215), Rosler, Martha (p.222), Schifano, Mario (p.223), Self, Colin (p.224), Tajiri, Thinkichi (p.228), Tanaami, Keiichi (p.229), Tilson, Joe (p.231), Vardea, Chryssa (p.233), Yokoo, Tadanori (p.234), Zelibska, Jana (p.235) and Zielinski, Jerzy (p.236).