The Halogen Bond in Weakly Bonded Complexes and the Consequences for Aromaticity and Spin-Orbit Coupling.

The halogen bond complexes CF3X⋯Y and C2F3X⋯Y, with Y = furan, thiophene, selenophene and X = Cl, Br, I, have been studied by using DFT and CCSD(T) in order to understand which factors govern the interaction between the halogen atom X and the aromatic ring. We found that PBE0-dDsC/QZ4P gives an adequate description of the interaction energies in these complexes, compared to CCSD(T) and experimental results. The interaction between the halogen atom X and the π-bonds in perpendicular orientation is stronger than the interaction with the in-plane lone pairs of the heteroatom of the aromatic cycle. The strength of the interaction follows the trend Cl < Br < I; the chalcogenide in the aromatic ring nor the hybridization of the C−X bond play a decisive role. The energy decomposition analysis shows that the interaction energy is dominated by all three contributions, viz., the electrostatic, orbital, and dispersion interactions: not one factor dominates the interaction energy. The aromaticity of the ring is undisturbed upon halogen bond formation: the π-ring current remains equally strong and diatropic in the complex as it is for the free aromatic ring. However, the spin-orbit coupling between the singlet and triplet π→π* states is increased upon halogen bond formation and a faster intersystem crossing between these states is therefore expected.

Explicit IMF B y -Dependence of Energetic Protons and the Ring Current.

The most important parameter driving the solar wind-magnetosphere interaction is the southward (B z ) component of the interplanetary magnetic field (IMF). While the dawn-dusk (B y ) component of the IMF is also known to play an important role, its effects are usually assumed to be independent of its sign. Here we demonstrate for the first time a seasonally varying, explicit IMF B y -dependence of the ring current and Dst index. Using satellite observations and a global magnetohydrodynamic model coupled with a ring current model, we show that for a fixed level of solar wind driving the flux of energetic magnetospheric protons and the growth-rate of the ring current are greater for B y  < 0 (B y  > 0) than for B y  > 0 (B y  < 0) in Northern Hemisphere summer (winter). While the physical mechanism of this explicit B y -effect is not yet fully understood, our results suggest that IMF B y modulates magnetospheric convection and plasma transport in the inner magnetosphere.

Correspondence on "How Aromatic Are Molecular Nanorings? The Case of a Six-Porphyrin Nanoring".

A recent Research Article in this journal by Matito and co-workers claimed that none of the oxidation states of a butadiyne-linked six-porphyrin nanoring exhibit global aromaticity or antiaromaticity. Here we show that this conclusion is incorrect. Experimental data from NMR spectroscopy for a whole family of nanorings provide strong evidence for global ring currents. The NMR data reveal these ring currents directly, without needing analysis by density functional theory (DFT). Furthermore, DFT calculations reproduce the experimental results when a suitable functional is used.

Structure, stability and bonding of the leapfrog B24 0 ,±1,±2.

Two new structural motifs of the B24 clusters are constructed by use of the leapfrog transformation. The resulting leapfrog B24 has either a bowl shape with a square vacancy or a quasi-planar 2D close-packed triangular boron sheet. The neutral and ionic forms of the latter are found to be more stable than their homologous leapfrog bowl clusters, with the exception of the dicationic B24 +2 . While the leapfrog isomer is less stable than the tubular double ring in the neutral state, it becomes competitive in some ionic states. The nucleus independent chemical shift, electron localization function, ring current maps and the electronic structure of leapfrog B24 clusters reveal them to behave as aromatics.

Interplay of Hückel and Möbius Aromaticity in Metal-Metal Quintuple Bonded Complexes of Cr, Mo, and W with Amidinate Ligand: Ab†initio DFT and Multireference Analysis*.

The aromaticity of metal-metal quintuple bonded complexes of the type M2 L2 (M=Cr, Mo, and W; L=amidinate) are studied employing gauge including magnetically induced ring current (GIMIC) analysis and electron density of delocalized bonds (EDDB). It is found that the complexes possess two types of aromaticity: i) Hückel aromaticity through delocalization of ligand π electrons with metal-metal δ-bond-forming 6 conjugated electrons (4π and 2δ) ring; ii) Craig-Möbius aromaticity through delocalization of π electrons of both the ligands with metal d-orbitals in Craig type orientation forming 10π electrons ring with a double twist. Extended transition state natural orbital chemical valence (ETS-NOCV) and canonical molecular orbital natural chemical shielding (CMO-NCS) analysis confirm the Craig-Möbius type arrangement of the orbitals. Furthermore, the unprecedented Hückel and Möbius type aromaticity is confirmed from the plot of the current pathways using 3D line integral convolution (3D-LIC) plots. The metal-metal bond order also increases down the group as justified from the complete active space self-consistent field (CASSCF) analysis. Due to an increase in the π and δ electron conjugation, both the Hückel and Möbius aromaticity increase down the group.

Auroral Energy Flux and Joule Heating Derived From Global Maps of Field-Aligned Currents.

We calculate auroral energy flux and Joule heating in the high-latitude ionosphere for 27 geomagnetically active days using two-dimensional maps of field-aligned currents determined by the Active Magnetosphere and Planetary Response Experiment. The energy input to the ionosphere due to Joule heating increases more rapidly with geomagnetic activity than that due to precipitating particles. The energy flux varies more smoothly with time than Joule heating, which is impulsive in nature on time scales from minutes to tens of minutes. These impulsive events correlate well with recoveries in the Sym-H index, with the maximum correlation when compared to Sym-H recoveries 70 min later. Because of prior studies that have associated transient recoveries of Sym-H with substorm expansions, the delay found here suggests that dissipation of energy in the ionosphere occurs during the substorm growth phase prior to the release of magnetic energy caused by diversion of tail currents.

Benzonorcorrole NiII Complexes: Enhancement of Paratropic Ring Current and Singlet Diradical Character by Benzo-Fusion.

Fused benzene rings to antiaromatic compounds generally improve their stability but attenuate their antiaromaticity. The opposite case is now reported. NiII benzonorcorroles were synthesized and the effect of benzo-fusion on the antiaromaticity was elucidated. The benzo-fusion resulted in significant decrease of the HOMO-LUMO gaps and enhancement of the paratropic ring current effect. Furthermore, the introduction of the benzo groups induced singlet diradical character in the antiaromatic porphyrinoid.

From C(58) to C(62) and back: Stability, structural similarity, and ring current.

An increasing number of observations show that non-classical isomers may play an important role in the formation of fullerenes and their exo- and endo-derivatives. A quantum-mechanical study of all classical isomers of C58 , C60 , and C62 , and all non-classical isomers with at most one square or heptagonal face, was carried out. Calculations at the B3LYP/6-31G* level show that the favored isomers of C58 , C60 , and C62 have closely related structures and suggest plausible inter-conversion and growth pathways among low-energy isomers. Similarity of the favored structures is reinforced by comparison of calculated ring currents induced on faces of these polyhedral cages by radial external magnetic fields, implying patterns of magnetic response similar to those of the stable, isolated-pentagon C60 molecule. © 2016 Wiley Periodicals, Inc.

Theoretical strategies toward stabilization of singlet remote N-heterocyclic carbenes.

Theoretical investigations predict that the singlet states of ylide-substituted remote carbenes are significantly stable and comparable to those of experimentally known NHCs. They are also found to be strongly σ-donating in nature as evident from an evaluation of the carbonyl stretching frequencies (νCO ) of their complexes with the [Rh(CO)2 Cl] fragment. NICS and QTAIM based bond magnetizability calculations indicate the presence of cyclic electron delocalization in majority of the molecules. © 2016 Wiley Periodicals, Inc.

Conformational transformation of ascidiacyclamide analogues induced by incorporating enantiomers of phenylalanine, 1-naphthylalanine or 2-naphthylalanine.

We designed five ascidiacyclamide analogues [cyclo(-Xxx(1) -oxazoline(2) -d-Val(3) -thiazole(4) -l-Ile(5) -oxazoline(6) -d-Val(7) -thiazole(8) -)] incorporating l-1-naphthylalanine (l-1Nal), l-2-naphthylalanine (l-2Nal), d-phenylalanine (d-Phe), d-1-naphthylalanine (d-1Nal) or d-2-naphthylalanine (d-2Nal) into the Xxx(1) position of the peptide. The conformations of these analogues were then examined using (1) H NMR, CD spectroscopy, and X-ray diffraction. These analyses suggested that d-enantiomer-incorporated ASCs [(d-Phe), (d-1Nal), and (d-2Nal)ASC] transformed from the folded to the open structure in solution more easily than l-enantiomer-incorporated ASCs [(l-Phe), (l-1Nal), and (l-2Nal)ASC]. Structural comparison of the two analogues containing isomeric naphthyl groups showed that the 1-naphthyl isomer induced a more stable open structure than the 2-naphthyl isomer. In particular, [d-1Nal]ASC showed the most significant transformation from the folded to the open structure in solution, and exhibited the strongest cytotoxicity toward HL-60 cells.

Bonding and singlet-triplet gap of silicon trimer: effects of protonation and attachment of alkali metal cations.

We revisit the singlet-triplet energy gap (ΔE(ST)) of silicon trimer and evaluate the gaps of its derivatives by attachment of a cation (H(+), Li(+), Na(+), and K(+)) using the wavefunction-based methods including the composite G4, coupled-cluster theory CCSD(T)/CBS, CCSDT and CCSDTQ, and CASSCF/CASPT2 (for Si3) computations. Both (1)A1 and (3)A2' states of Si3 are determined to be degenerate. An intersystem crossing between both states appears to be possible at a point having an apex bond angle of around α = 68 ± 2° which is 16 ± 4 kJ/mol above the ground state. The proton, Li(+) and Na(+) cations tend to favor the low-spin state, whereas the K(+) cation favors the high-spin state. However, they do not modify significantly the ΔE(ST). The proton affinity of silicon trimer is determined as PA(Si3) = 830 ± 4 kJ/mol at 298 K. The metal cation affinities are also predicted to be LiCA(Si3) = 108 ± 8 kJ/mol, NaCA(Si3) = 79 ± 8 kJ/mol and KCA(Si3) = 44 ± 8 kJ/mol. The chemical bonding is probed using the electron localization function, and ring current analyses show that the singlet three-membered ring Si3 is, at most, nonaromatic. Attachment of the proton and Li(+) cation renders it anti-aromatic.

Cyclophanes containing bowl-shaped aromatic chromophores: three isomers of anti-[2.2](1,4)subphthalocyaninophane.

The connection of bowl-shaped aromatic boron subphthalocyanines with anti-[2.2]paracyclophane resulted in the first observation of electronic communication between convex and concave surfaces. Three isomers of anti-[2.2](1,4)subphthalocyaninophane, described as concave-concave (CC), convex-concave (CV), and convex-convex (VV) according to the orientation of the subphthalocyanine units, were synthesized and characterized by various spectroscopic techniques, including (1) H NMR, electronic absorption, fluorescence, and magnetic circular dichroism spectroscopy and X-ray crystallography, together with molecular-orbital calculations. On going from the CC system to CV and further to VV, the Q band broadened and finally split as a result of through-space expansion of the conjugated systems, which were also reproduced theoretically.

Modulating the structure of phenylalanine-incorporated ascidiacyclamide through fluorination.

We designed four fluorinated Phe-incorporated ascidiacyclamide ([Phe]ASC) analogs, (cyclo(-Xxx1-oxazoline2-D-Val3-thiazole4-Ile5-oxazoline6-D-Val7-thiazole8-)), [(4-F)Phe]ASC (Xxx1: 4-fluorophenylalanine), [(3,5-F2)Phe]ASC (Xxx1: 3,5-difluorophenylalanine), [(3,4,5-F3)Phe]ASC (Xxx1: 3,4,5-trifluorophenylalanine) and [(F5)Phe]ASC (Xxx1: pentafluorophenylalanine), to modulate the π-electron density of the aromatic ring of the Phe residue. X-ray diffraction analysis, ¹H NMR and CD spectra all suggested that the interactions between the benzene ring of the Xxx1 residue and the alkyl groups of oxazoline2 contribute to the stability of the folded structure of these analogs. Substituting fluorines for the hydrogens progressively weakened those interactions through reducing the π-electron density, thereby mediating transformation from the folded to square structure. As a result, [(F5)Phe]ASC preferred the square form more than the other analogs did. Also contributing to the preference for the square form may be the hindrance of the rotation around the Cα-Cß bond by the two ortho-fluoro substituents of [(F5)Phe]ASC. These findings demonstrate that the structure of ASC can be modulated by using fluorine as an electron-withdrawing group.

Resonance assignments of cytochrome MtoD from the extracellular electron uptake pathway of sideroxydans lithotrophicus ES-1.

The contribution of Fe(II)-oxidizing bacteria to iron cycling in freshwater, groundwater, and marine environments has been widely recognized in recent years. These organisms perform extracellular electron transfer (EET), which constitutes the foundations of bioelectrochemical systems for the production of biofuels and bioenergy. It was proposed that the Gram-negative bacterium Sideroxydans lithotrophicus ES-1 oxidizes soluble ferrous Fe(II) at the surface of the cell and performs EET through the Mto redox pathway. This pathway is composed by the periplasmic monoheme cytochrome MtoD that is proposed to bridge electron transfer between the cell exterior and the cytoplasm. This makes its functional and structural characterization, as well as evaluating the interaction process with its physiological partners, essential for understanding the mechanisms underlying EET. Here, we report the complete assignment of the heme proton and carbon signals together with a near-complete assignment of 1H, 13C and 15N backbone and side chain resonances for the reduced, diamagnetic form of the protein. These data pave the way to identify and structurally map the molecular interaction regions between the cytochrome MtoD and its physiological redox partners, to explore the EET processes of S. lithotrophicus ES-1.

Radiation Belt Storm Probes Ion Composition Experiment (RBSPICE) Revisited: In-Flight Calibrations, Lessons Learned and Scientific Advances.

The Radiation Belt Storm Probes Ion Composition Experiment (RBSPICE) on both the Van Allen Probes spacecraft is a time-of-flight versus total energy instrument that provided ion composition data over the ring current energy (∼7 keV to ∼1 MeV), and electrons over the energy range ∼25 keV to ∼1 MeV throughout the duration of the mission (2012 - 2019). In this paper we present instrument calibrations, implemented after the Van Allen Probes mission was launched. In particular, we discuss updated rate dependent corrections, possible contamination by "accidentals" rates, and caveats concerning the use of certain products. We also provide a summary of the major advances in ring current science, obtained from RBSPICE observations, and their implications for the future of inner magnetosphere exploration.

Identification of ring current proton precipitation driven by scattering of electromagnetic ion cyclotron waves.

Among the most intense emissions in the Earth's magnetosphere, electromagnetic ion cyclotron (EMIC) waves are regarded as a critical candidate contributing to the precipitation losses of ring current protons, which however lacks direct multi-point observations to establish the underlying physical connection. Based upon a robust conjunction between the satellite pair of Van Allen Probe B and NOAA-19, we perform a detailed analysis to capture simultaneous enhancements of EMIC waves and ring current proton precipitation. By assuming that the ring current proton precipitation is mainly caused by EMIC wave scattering, we establish a physical model between the wave-driven proton diffusion and the ratio of precipitated-to-trapped proton count rates, which is subsequently applied to infer the intensity of EMIC waves required to cause the observed proton precipitation. Our simulations indicate that the model results of EMIC wave intensity, obtained using either the observed or empirical Gaussian wave frequency spectrum, are consistent with the wave observations, within a factor of 1.5. Our study therefore strongly supports the dominant contribution of EMIC waves to the ring current proton precipitation, and offers a valuable means to construct the global profile of EMIC wave intensity using low-altitude NOAA POES proton measurements, which generally have a broad L-shell coverage and high time resolution in favor of near-real-time conversion of the global EMIC wave distribution.

A New Mechanism for Early-Time Plasmaspheric Refilling: The Role of Charge Exchange Reactions in the Transport of Energy and Mass Throughout the Ring Current-Plasmasphere System.

Cold H+ produced via charge exchange reactions between ring current ions and exospheric neutral hydrogen constitutes an additional source of cold plasma that further contributes to the plasmasphere and affects the plasma dynamics in the Earth's magnetosphere system; however, its production and associated effects on the plasmasphere dynamics have not been fully assessed and quantified. In this study, we perform numerical simulations mimicking an idealized three-phase geomagnetic storm to investigate the role of heavy ion composition in the ring current (O+ vs. N+) and exospheric neutral hydrogen density in the production of cold H+ via charge exchange reactions. It is found that ring current heavy ions produce more than 50% of the total cold H+ via charge exchange reactions, and energetic N+ is more efficient in producing cold H+ via charge exchange reactions than O+. Furthermore, the density structure of the cold H+ is highly dependent on the mass of the parent ion; that is, cold H+ deriving from charge exchange reactions involving energetic O+ with neutral hydrogen, populates the lower L-shells, while cold H+ deriving from charge exchange reactions involving energetic N+ with neutral hydrogen populates the higher L-shells. In addition, the density of cold H+ produced via charge exchange reactions involving N+ can be peak at values up to one order of magnitude larger than the local plasmaspheric density, suggesting that solely considering the supply of cold plasma from the ionosphere to the plasmasphere can lead to a significant underestimation of plasmasphere density.

Science of the Van Allen Probes Science Operations Centers.

The Van Allen Probes mission operations materialized through a distributed model in which operational responsibility was divided between the Mission Operations Center (MOC) and separate instrument specific SOCs. The sole MOC handled all aspects of telemetering and receiving tasks as well as certain scientifically relevant ancillary tasks. Each instrument science team developed individual instrument specific SOCs proficient in unique capabilities in support of science data acquisition, data processing, instrument performance, and tools for the instrument team scientists. In parallel activities, project scientists took on the task of providing a significant modeling tool base usable by the instrument science teams and the larger scientific community. With a mission as complex as Van Allen Probes, scientific inquiry occurred due to constant and significant collaboration between the SOCs and in concert with the project science team. Planned cross-instrument coordinated observations resulted in critical discoveries during the seven-year mission. Instrument cross-calibration activities elucidated a more seamless set of data products. Specific topics include post-launch changes and enhancements to the SOCs, discussion of coordination activities between the SOCs, SOC specific analysis software, modeling software provided by the Van Allen Probes project, and a section on lessons learned. One of the most significant lessons learned was the importance of the original decision to implement individual team SOCs providing timely and well-documented instrument data for the NASA Van Allen Probes Mission scientists and the larger magnetospheric and radiation belt scientific community.

NMR studies of adsorption and diffusion in porous carbonaceous materials.

Porous carbonaceous materials have many important industrial applications including energy storage, water purification, and adsorption of volatile organic compounds. Most of their applications rely upon the adsorption of molecules or ions within the interior pore volume of the carbon particles. Understanding the behaviour and properties of adsorbate species on the molecular level is therefore key for optimising porous carbon materials, but this is very challenging owing to the complexity of the disordered carbon structure and the presence of multiple phases in the system. In recent years, NMR spectroscopy has emerged as one of the few experimental techniques that can resolve adsorbed species from those outside the pore network. Adsorbed, or "in-pore" species are shielded with respect to their free (or "ex-pore") counterparts. This shielding effect arises primarily due to ring currents in the carbon structure in the presence of a magnetic field, such that the observed chemical shift differences upon adsorption are independent of the observed nucleus to a first approximation. Theoretical modelling has played an important role in rationalising and explaining these experimental observations. Together, experiments and simulations have enabled a large amount of information to be gained on the adsorption and diffusion of adsorbed species, as well as on the structural and magnetic properties of the porous carbon adsorbent. Here, we review the methodological developments and applications of NMR spectroscopy and related modelling in this field, and provide perspectives on possible future applications and research directions.

A study on the aromaticity and magnetic properties of N-confused porphyrins.

In this paper, topological resonance energy (TRE) methods were used to describe the global aromaticity of nitrogen confused porphyrin (NCP) isomers. The TRE results show that all NCP isomers exhibit lower aromaticity than the normal porphyrins, and their aromaticity decreases as the number of confused pyrrole rings in the molecule increases. In the NCPs, global aromaticity decreases as the distance between the nitrogen atoms increases. The bond resonance energy (BRE) and circuit resonance energy (CRE) indices were applied to study local aromaticity and conjugated pathways. Both the BRE and CRE indices revealed that individual pyrrolic subunits maintain their strong aromatic character and are the main source of global aromaticity. Ring currents (RC) were analysed using the Hückel-London model. RC results revealed that the macrocyclic electron conjugation pathway is the main source of diatropicity. As the number of confused pyrrole rings in the molecule increases, its diatropicity gradually decreases. In the confused pyrrole rings of the NCP isomers, the diatropic RC passing through the ß-positions is always weaker than that passing through the inner sections. This is unrelated to the location of the protonated or non-protonated nitrogen atom at the periphery of the molecule and must be ascribed to the unique properties of the confused pyrrole rings.