Novel charge transfer supramolecular assemblies with Keggin anions and 2-amino-5-nitropyridine

Several novel compounds with the non-linear optical chromophore 2-amino-5-nitropyridine (2A5NP) and Keggin polyoxoanions (alpha-isomers), having the general formula (2A5NP)(m)H-n[XM12O40]center dot xH(2)O, M = Mo, W, were synthesised. Compounds were obtained with X = P, n = 3, m = 3 and 4 and X = Si, n = m = 4 ( x = 2 - 6). Thus, for each of the anions [PMo12O40](3-) and [PW12O40](3-) two different compounds were obtained, with the same anion and organic counterpart but with a different stoichiometric ratio. These presented different charge transfer properties and thermal stability. All compounds were characterised by spectroscopic and analytical techniques. The single crystal X-ray diffraction structure of (2A5NP)(4)H-3[PMo12O40]center dot 2.5H(2)O center dot 0.5C(2)H(5)OH showed that the water solvent molecules and the organic chromophores are assembled via infinite one-dimensional chains of hydrogen bonds with formation of open channels, which accommodate [ PMo12O40] 3- and ethanol solvent molecules.

Facile photoinduced charge separation through a cyanoacetylide bridge in a heterobimetallic Fe(II)-Re(I) complex

Photoinduced Fe-to-bpy charge transfer in [{Cp(dppe)Fe}-(mu-C CC N){Re(CO)(3)(bpy)}]PF6 has been observed by ps-TRIR spectroscopy, supported by UV-Vis/IR spectroelectrochemistry and DFT calculations.

Charge transfer in Cr adsorption and reaction at the rutile TiO2(110) surface

The rutile TiO2(110) surface has been doped with sub-monolayer metallic Cr, which oxidises and donates charge to specific surface Ti ions. X-Ray and ultra violet photoemission spectroscopy and first principles density functional theory with Hubbard U are used to assign the oxidation states of Cr and surface Ti and we find that Cr2+ forms on bridging oxygen ions and a 5-fold coordinated surface Ti atom is reduced to Ti3+ and the Cr ions readily react with oxygen (to Cr3+), which leads to depletion of surface Ti3+ 3d electrons.

Ultrafast charge separation in a photoreactive rhenium-appended porphyrin assembly monitored by picosecond transient infrared spectroscopy

Rhenium(bipyridine)(tricarbonyl)(picoline) units have been linked covalently to tetraphenylmetalloporphyrins of magnesium and zinc via an amide bond between the bipyridine and one phenyl substituent of the porphyrin. The resulting complexes, abbreviated as [Re(CO)(3)(Pic)Bpy-MgTPP][OTf] and [Re(CO)(3)(Pic)Bpy-ZnTPP][OTf], exhibit no signs of electronic interaction between the Re(CO)(3)(bpy) units and the metalloporphyrin units in their ground states. However, emission spectroscopy reveals solvent-dependent quenching of porphyrin emission on irradiation into the long-wavelength absorption bands localized on the porphyrin. The characteristics of the excited states have been probed by picosecond time-resolved absorption (TRVIS) spectroscopy and time-resolved infrared (TRIR) spectroscopy in nitrile solvents. The presence of the charge-separated state involving electron transfer from MgTPP or ZnTPP to Re(bpy) is signaled in the TRIR spectra by a low-frequency shift in the nu(CO) bands of the Re(CO)(3) moiety similar to that observed by spectroelectrochemical reduction. Long-wavelength excitation of [Re(CO)(3)(Pic)Bpy-MTPP][OTf] results in characteristic TRVIS spectra of the S-1 state of the porphyrin that decay with a time constant of 17 ps (M = Mg) or 24 ps (M = Zn). The IR bands of the CS state appear on a time scale of less than 1 ps (Mg) or ca. 5 ps (Zn) and decay giving way to a vibrationally excited (i.e., hot) ground state via back electron transfer. The IR bands of the precursors recover with a time constant of 35 ps (Mg) or 55 ps (Zn). The short lifetimes of the charge-transfer states carry implications for the mechanism of reaction in the presence of triethylamine.

Redox control of light-induced charge separation in a transition metal cluster: photochemistry of a methyl viologen-substituted [Os-3(CO)10(a-diimine)] cluster

Sub)picosecond transient absorption (TA) and time-resolved infrared (TRIR) spectra of the cluster [OS3(CO)(10-) (AcPy-MV)](2+) (the clication AcPy-MV = Acpy-MV2+ = [2-pyridylacetimine-N-(2-(1'-methyl-4,4'-bipyridine-1,1'-diium-1-yl) ethyl)] (PF6)(2)) (1(2+)) reveal that photoinduced electron transfer to the electron-accepting 4,4'-bipyridine-1,1'diium (MV2+) moiety competes with the fast relaxation of the initially populated sigmapi* excited state of the cluster to the ground state and/or cleavage of an Os-Os bond. The TA spectra of cluster 12 in acetone, obtained by irradiation into its lowest-energy absorption band, show the characteristic absorptions of the one-electron-reduced MV*(+) unit at 400 and 615 nm, in accordance with population of a charge-separated (CS) state in which a cluster-core electron has been transferred to the lowest pi* orbital of the remote MV2+ unit. This assignment is confirmed by picosecond TRIR spectra that show a large shift of the pilot highest-frequency nu(CO) band of 1(2+) by ca. +40 cm(-1), reflecting the photooxidation of the cluster core. The CS state is populated via fast (4.2 x 10(11) s(-1)) and efficient (88%) oxidative quenching of the optically populated sigmapi* excited state and decays biexponentially with lifetimes of 38 and 166 ps (1:2:1 ratio) with a complete regeneration of the parent cluster. About 12% of the cluster molecules in the sigmapi* excited state form long-lived open-core biradicals. In strongly coordinating acetonitrile, however, the cluster core-to-MV2+ electron transfer in cluster 12+ results in the irreversible formation of secondary photoproducts with a photooxidized cluster core. The photochemical behavior of the [Os-3(CO)(10)(alpha-diimine-MV)](2+) (donor-acceptor) dyad can be controlled by an externally applied electronic bias. Electrochemical one-electron reduction of the MV2+ moiety prior to the irradiation reduces its electron-accepting character to such an extent that the photoinduced electron transfer to MV*+ is no longer feasible. Instead, the irradiation of reduced cluster 1(.)+ results in the reversible formation of an open-core zwitterion, the ultimate photoproduct also observed upon irradiation of related nonsubstituted clusters [Os-3(CO)(10)(alpha-diimine)] in strongly coordinating solvents such as acetonitrile.

Effect of headgroup size, charge, and solvent structure on polymer−micelle interactions, studied by molecular dynamics simulations

We performed atomistic molecular dynamics simulations of anionic and cationic micelles in the presence of poly(ethylene oxide) (PEO) to understand why nonionic water-soluble polymers such as PEO interact strongly with anionic micelles but only weakly with cationic micelles. Our micelles include sodium n-dodecyl sulfate (SDS), n-dodecyl trimethylammonium chloride (DTAC), n-dodecyl ammonium chloride (DAC), and micelles in which we artificially reverse the sign of partial charges in SDS and DTAC. We observe that the polymer interacts hydrophobically with anionic SDS but only weakly with cationic DTAC and DAC, in agreement with experiment. However, the polymer also interacts with the artificial anionic DTAC but fails to interact hydrophobically with the artificial cationic SDS, illustrating that large headgroup size does not explain the weak polymer interaction with cationic micelles. In addition, we observe through simulation that this preference for interaction with anionic micelles still exists in a dipolar "dumbbell" solvent, indicating that water structure and hydrogen bonding alone cannot explain this preferential interaction. Our simulations suggest that direct electrostatic interactions between the micelle and polymer explain the preference for interaction with anionic micelles, even though the polymer overall carries no net charge. This is possible given the asymmetric distribution of negative charges on smaller atoms and positive charges oil larger units in the polymer chain.

Correlation between regioselectivity and site charge in propene polymerisation catalysed by metallocene

The reactions of propene with [Zr(cyclopentadienyl)(2)Me](+) have been investigated using density functional theory in order to study the correlation between regioselectivity and site charge in propene polymerisation. The reaction paths of the 1,2 and 2,1 additions of the methyl group to propene have been established. The geometries and energies of the reactants, transition states and products have been obtained using both PBEPBE/LANL2DZ and B3LYP/LANL2DZ methodologies. The results with both density functionals show that the activation energy for 1,2-insertion is lower than that for 2,1-insertion (Fig. 5) and this is consistent with the experiment results. Also for both density functionals, the difference of the thermal dynamic driving forces between the 2,1 product named 2-21 and the 1,2 product named 2-12 is significantly lower than the difference between the energy barriers. It is noted that in the reactants, the Mulliken partial charge on the central carbon atom C2 is positive and it can be concluded that 1,2-insertion is favoured because it can proceed via a cationic reaction.

Charge measurements in stratiform cloud from a balloon based sensor

Abstract. The electrification of stratiform clouds has is little investigated in comparison with thunderstorms and fair weather atmospheric electricity. Theory indicates that, at the upper and lower horizontal boundaries of layer clouds, charging will arise from vertical flow of cosmogenic ions in the global atmospheric electric circuit. Charge is transferred to droplets and particles, affecting cloud microphysical processes such as collision and droplet activation. Due to the lack of in-situ measurements, the magnitude and distribution of charge in stratiform clouds is not well known. A sensitive, inexpensive, balloon borne charge sensor has been developed to make in-situ measurements of edge charging in stratiform cloud using a standard meteorological radiosonde system. The charge sensor has now been flown through over 20 stratiform clouds and frequently detected charge up to 200 pC m-3 near cloud edges. These results are compared with measurements from the same sensor used to investigate charge in particle layers, such as volcanic ash from the Eyjafjallajökull eruption, and Saharan dust in the Cape Verde Isles. 1.

Towards a European tephrochronological framework for Termination 1 and the Early Holocene

The record of deposition of tephras in Europe and the North Atlantic during the period 18.5–8.0 ¹⁴C ka BP (the Last Termination and Early Holocene) is reviewed. Altogether, 34 tephras originating from four main volcanic provinces (Iceland, the Eifel district, the Massif Central and Italy) have been identified so far in geological sequences spanning this time–interval. Most of the records have been based, until very recently, on observations of visible layers of tephras. Here, we report on the potential for extending the areas over which some of the tephras can be traced by the search for layers of micro–tephra, which are not visible to the naked eye, and on the use of geochemical methods to correlate them with known tephra horizons. This approach has greatly extended the area in Northern Europe over which the Vedde Ash can be traced. The same potential exists in southern Europe, which is demonstrated for the first time by the discovery of a distinct layer of micro–tephra of the Neapolitan Yellow Tuff in a site in the Northern Apennines in Italy, far to the north of the occurrences of visible records of this tephra. The paper closes by considering the potential for developing a robust European tephrostratigraphy to underpin the chronology of records of the Last Termination and Early Holocene, thereby promoting a better understanding of the nature, timing and environmental effects of the abrupt climatic changes that characterized this period.

Last charge of the knights? Iraq, Afghanistan and the special relationship

At the heart of the ‘special relationship’ ideology, there is supposed to be a grand bargain. In exchange for paying the ‘blood price’ as America's ally, Britain will be rewarded with exceptional influence over American foreign policy and its strategic behaviour. Soldiers and statesman continue to articulate this idea. Since 9/11, the notion of Britain playing ‘Greece’ to America's ‘Rome’ gained new life thanks to Anglophiles on both sides of the Atlantic. One potent version of this ideology was that the more seasoned British would teach Americans how to fight ‘small wars’ in Iraq and Afghanistan, thereby bolstering their role as tutor to the superpower. Britain does derive benefits from the Anglo-American alliance and has made momentous contributions to the wars in Afghanistan and Iraq. Yet British solidarity and sacrifices have not purchased special influence in Washington. This is partly due to Atlanticist ideology, which sets Britain unrealistic standards by which it is judged, and partly because the notion of ‘special influence’ is misleading as it loses sight of the complexities of American policy-making. The overall result of expeditionary wars has been to strain British credibility in American eyes and to display its lack of consistent influence both over high policy and the design and execution of US military campaigns. While there may be good arguments in favour of the UK continuing its efforts in Afghanistan, the notion that the war fortifies Britain's vicarious world status is a dangerous illusion that leads to repeated overstretch and disappointment. Now that Britain is in the foothills of a strategic defence review, it is important that the British abandon this false consciousness.

Service charge management

Service Charge Management is an area of concern to property managers acting for both property occupiers and investors. This paper reviews the background to service charge management in the UK, and examines, by means of a survey, the current state of service charge practice in the surveying profession.

Climate variability in the southwest Pacific during the Last Termination (20-10 kyr BP)

The degree to which palaeoclimatic changes in the Southern Hemisphere co-varied with events in the high latitude Northern Hemisphere during the Last Termination is a contentious issue, with conflicting evidence for the degree of ‘teleconnection’ between different regions of the Southern Hemisphere. The available hypotheses are difficult to test robustly, however, because there are few detailed palaeoclimatic records in the Southern Hemisphere. Here we present climatic reconstructions from the southwestern Pacific, a key region in the Southern Hemisphere because of the potentially important role it plays in global climate change. The reconstructions for the period 20–10 kyr BP were obtained from five sites along a transect from southern New Zealand, through Australia to Indonesia, supported by 125 calibrated 14C ages. Two periods of significant climatic change can be identified across the region at around 17 and 14.2 cal kyr BP, most probably associated with the onset of warming in the West Pacific Warm Pool and the collapse of Antarctic ice during Meltwater Pulse-1A, respectively. The severe geochronological constraints that inherently afflict age models based on radiocarbon dating and the lack of quantified climatic parameters make more detailed interpretations problematic, however. There is an urgent need to address the geochronological limitations, and to develop more precise and quantified estimates of the pronounced climate variations that clearly affected this region during the Last Termination.

Lightning-induced extensive charge sheets provide long range electrostatic thunderstorm detection

By combining electrostatic measurements of lightning-induced electrostatic field changes with radio frequency lightning location, some field changes from exceptionally distant lightning events are apparent which are inconsistent with the usual inverse cube of distance. Furthermore, by using two measurement sites, a transition zone can be identified beyond which the electric field response reverses polarity. For these severe lightning events, we infer a horizontally extensive charge sheet above a thunderstorm, consistent with a mesospheric halo of several hundred kilometers’ extent.

Impact of oceanic processes on the carbon cycle during the last termination

During the last termination (from ~18 000 years ago to ~9000 years ago), the climate significantly warmed and the ice sheets melted. Simultaneously, atmospheric CO2 increased from ~190 ppm to ~260 ppm. Although this CO2 rise plays an important role in the deglacial warming, the reasons for its evolution are difficult to explain. Only box models have been used to run transient simulations of this carbon cycle transition, but by forcing the model with data constrained scenarios of the evolution of temperature, sea level, sea ice, NADW formation, Southern Ocean vertical mixing and biological carbon pump. More complex models (including GCMs) have investigated some of these mechanisms but they have only been used to try and explain LGM versus present day steady-state climates. In this study we use a coupled climate-carbon model of intermediate complexity to explore the role of three oceanic processes in transient simulations: the sinking of brines, stratification-dependent diffusion and iron fertilization. Carbonate compensation is accounted for in these simulations. We show that neither iron fertilization nor the sinking of brines alone can account for the evolution of CO2, and that only the combination of the sinking of brines and interactive diffusion can simultaneously simulate the increase in deep Southern Ocean δ13C. The scenario that agrees best with the data takes into account all mechanisms and favours a rapid cessation of the sinking of brines around 18 000 years ago, when the Antarctic ice sheet extent was at its maximum. In this scenario, we make the hypothesis that sea ice formation was then shifted to the open ocean where the salty water is quickly mixed with fresher water, which prevents deep sinking of salty water and therefore breaks down the deep stratification and releases carbon from the abyss. Based on this scenario, it is possible to simulate both the amplitude and timing of the long-term CO2 increase during the last termination in agreement with ice core data. The atmospheric δ13C appears to be highly sensitive to changes in the terrestrial biosphere, underlining the need to better constrain the vegetation evolution during the termination.