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A masked amine building block is used to synthesize an organic cage that is exo-functionalized with one terpy group. Two exo-functionalized cages can be combined via iron-terpy coordination resulting in a cage dumbbell.

A conceptual approach for the synthesis of quasi‐heteroleptic complexes with properly endo‐functionalized cages as ligands is presented. The cage ligand reported here is of a covalent organic nature, it has been synthesized via a dynamic combinatorial chemistry approach, making use of a masked amine. Inspired by enzymatic active sites, the described system bears one carboxylate and two imidazole moieties as independent ligating units through which it is able to coordinate to transition metals. Analysis of the iron(II) complex in solution and the solid state validates the structure and shows that no undesired but commonly observed dimerization process takes place. The solid‐state structure shows a five‐coordinate metal center with the carboxylate bidentately bound to iron, which makes Fe@2 an unprecedentedly detailed structural model complex for this kind of non‐heme iron oxygenases. As, as confirmed by the crystal structure, sufficient space for other organic ligands is available, the biologically relevant ligand α‐ketoglutarate is implemented. We observe biomimetic reaction behavior towards dioxygen that opens studies investigating Fe@2 as a functional model complex., A cage compound is synthesized that is endo‐functionalized with one carboxylic acid and two imidazole moieties. These groups can cooperate with each other to coordinate to Zn(II) and Fe(II) resulting in biomimetic quasi‐heteroleptic transition‐metal‐cage complexes. Coordination of α‐ketoglutarate to the iron complex leads to an increase of its reactivity towards dioxygen.

C-H amination and amidation by catalytic nitrene transfer are well-established and typically proceed via electrophilic attack of nitrenoid intermediates. In contrast, the insertion of (formal) terminal nitride ligands into C-H bonds is much less developed and catalytic nitrogen atom transfer remains unknown. We here report the synthesis of a formal terminal nitride complex of palladium. Photocrystallographic, magnetic, and computational characterization support the assignment as an authentic metallonitrene (Pd-N) with a diradical nitrogen ligand that is singly bonded to Pd

An azide masked amine is used to obtain a cage of lower symmetry that possess one terpy-group in an

The optimized superconducting stellarator device Wendelstein 7-X (with major radius , minor radius , and plasma volume) restarted operation after the assembly of a graphite heat shield and 10 inertially cooled island divertor modules. This paper reports on the results from the first high-performance plasma operation. Glow discharge conditioning and ECRH conditioning discharges in helium turned out to be important for density and edge radiation control. Plasma densities of with central electron temperatures were routinely achieved with hydrogen gas fueling, frequently terminated by a radiative collapse. In a first stage, plasma densities up to were reached with hydrogen pellet injection and helium gas fueling. Here, the ions are indirectly heated, and at a central density of a temperature of with was transiently accomplished, which corresponds to with a peak diamagnetic energy of and volume-averaged normalized plasma pressure . The routine access to high plasma densities was opened with boronization of the first wall. After boronization, the oxygen impurity content was reduced by a factor of 10, the carbon impurity content by a factor of 5. The reduced (edge) plasma radiation level gives routinely access to higher densities without radiation collapse, e.g. well above line integrated density and central temperatures at moderate ECRH power. Both X2 and O2 mode ECRH schemes were successfully applied. Core turbulence was measured with a phase contrast imaging diagnostic and suppression of turbulence during pellet injection was observed.

Summary In contrast to its lighter congener N2, neutral diphosphorus with a P≡P triple bond is a highly reactive species observable only in the gas phase and by matrix isolation. Previous stabilization efforts with Lewis bases (e.g., carbenes) or by transition-metal coordination led to charge transfer to highly electrophilic P2 and thus to significant reduction of the bond order. Here, we report the crystallographic, spectroscopic, and quantum chemical characterization of the redox series [(μ2,η1:η1-P2){Pt(PNP)}2] (PNP = N(CHCHPtBu2)2), which features (P2)2–, (P2)⋅–, and (P2)0 as bridging ligands. Although common for N2, the stabilization as a neutral, triply bonded P≡P ligand is unprecedented for the heavier homolog. It was enabled by coordination of the dipnictogen to redox-inactive Lewis-acidic metal fragments and gave rise to the controlled release of P2 in the condensed phase.

The fundamental behavior of the W7-X island divertor under detached conditions, which has been theoretically predicted with the EMC3-Eirene code, is re-examined here under the experimental conditions achieved so far and compared with the first experimental results. Both simulations and experiments cover a range of divertor configurations and plasma parameters, and show the following common trends: (1) with rising impurity radiation, the target heat load decreases ‘uniformly’ over the entire target surface in the sense that both the peak and average heat loads can drop by an order of magnitude. Impurity radiation (mainly from intrinsic carbon) occurs primarily at the plasma edge and the resulting negative impact on the stored energy is less than 10%. (2) When the total radiation exceeds a critical level, the target particle flux (the recycling flux Γrecy) begins to fall and can drop by a factor of 3–5 at high radiation levels without an obvious indication of significant volume recombination. (3) While Γrecy decreases, the divertor neutral pressure continues to build up and reaches a maximum, at which point Γrecy has declined significantly. (4) During detachment, the electron temperature at the last closed flux surface falls in a way that is not quantitatively understandable from parallel classical heat conduction processes. This paper presents a physical explanation of the numerical/experimental results described above. Furthermore, using the EMC3-Eirene code as a diagnostic tool, we are able, apparently for the first time, to provide a full quantitative analysis of each transport channel in the island divertor, aiming to clarify how the island divertor plasma self-regulates to maintain particle, energy, and momentum balance under detached conditions.

The operational regimes in the first divertor campaign of W7-X were limited by unexpectedly high heat loads on certain baffle tiles. In the high-mirror configuration, a permanent hotspot on the baffle plate was detected by the thermographic system, which was further confirmed during the post-campaign inspections of the plasma-facing components. The maximum heat load on three baffle tiles reached about 4.5 MW m−2, which is almost an order of magnitude above its designed value of 0.5 MW m−2. The paper presents a detailed analysis to understand how the baffle plate, which is originally designed to screen the recycling neutrals and is therefore hidden from the hot plasma, can receive such a high heat load – a level that is expected for target plates. Three main causes have been identified: 1) the three baffle tiles are radially only about 5 mm away from a main heat channel towards a target, which is much shorter than the radial power decay length of several centimeters derived from the thermographic measurements in this region; 2) the three baffle tiles are intersected with field-lines of about 30 m length, which are long enough to collect considerable amount of heat via cross-field transport; 3) the baffle tiles have locally large grazing angles. In addition, the analysis method shown in this paper is of general use to estimate the heat flows in shadow areas of targets and thus to evaluate heat loads on the potentially critical components occurring in these areas, especially required for the design of complex 3D divertors like the one in W7-X.

A significant improvement of plasma parameters in the optimized stellarator W7-X is found after injections of frozen hydrogen pellets. The ion temperature in the post-pellet phase exceeds 3 keV with 5 MW of electron heating and the global energy confinement time surpasses the empirical ISS04-scaling. The plasma parameters realized in such experiments are significantly above those in comparable gas-fuelled discharges. In this paper, we present details of these pellet experiments and discuss the main plasma properties during the enhanced confinement phases. Local power balance is applied to show that the heat transport in post-pellet phases is close to the neoclassical level for the ion channel and is about a factor of two above that level for the combined losses. In comparable gas-fuelled discharges, the heat transport is by about ten times larger than the neoclassical level, and thus is largely anomalous. It is further observed that the improvement in the transport is related to the peaked density profiles that lead to a stabilization of the ion-scale turbulence.

The selective synthesis of purely organic cages offering hetero-sequenced functionalized cavities is demonstrated. The strategy to obtain these compounds is based on a stepwise approach using thermodynamically controlled imine condensations. To accomplish this, the amine building blocks offer additional azide functionalization, acting as masked amines enabling the synthesis of the desired cavities. This approach enables a precise control of interior functionalization, the substitution pattern and the cage size, which is demonstrated by the selective synthesis of four cages. The largest described cage has been investigated towards its ability for guest encapsulation and is able to selectively encapsulate functionalized arenes that offer a matching substitution pattern.

Observations on confinement in the first experimental campaign on the optimized Stellarator Wendelstein 7-X are summarized. In this phase W7-X was equipped with five inboard limiters only and thus the discharge length restricted to avoid local overheating. Stationary plasmas are limited to low densities

Controlled radiative power exhaust with impurity seeding has been demonstrated in island divertor configurations at the stellarator Wendelstein 7-X. Detachment has been established with neon (Ne) and nitrogen (N2) seeding for the price of a loss of ΔWp>-15% in the stored energy [1]. Ne seeding allows for sustained enhancement of edge radiation with (frad>80%) a prolonged decay of line emission of several tens of seconds after the end of the injection indicating high recycling of this noble gas at the carbon main plasma facing components (PFCs). In N2-seeded discharges, it is shown that a response of line emission and plasma parameters is in correlation to the puff duration, which indicates a higher level of absorption of this seeding gas in the PFCs. Continuous N2 seeding results in global cooling of the scrape-off layer (SOL) and decay of radiation over several seconds after the injection. These results have been obtained by local gas injection into one of the five independent island chains.Zeff increases from 1.2 to 2.1-2.2 at maximum radiation with both seeding gases and reduces after the injection only in the case of N2 seeding. Damping of the counter-streaming SOL island flows is in correlation with a reduction of the divertor particle fluxes in response to impurity seeding. A correlated reduction of density has been compensated by feedback-controlled divertor gas fueling. The controlled reduction of heat fluxes within this complex 3D edge island geometry is a very promising finding concerning detachment optimization in future scenarios with steady-state operation and metallic wall upgrades [2]. The significant features of the 3D distribution of radiative power losses and the effects on heat and particle fluxes have been recovered with EMC3-EIRENE simulations. Simulations with different island geometries and parameter scans have been investigated to resolve the dependencies of the radiative cooling effects and detachment transitions for Ne and N2 seeding. [1] F. Effenberg et al 2019 Nucl. Fusion 59 106020 [2] Y. Feng et al 2016 Nucl. Fusion 56 126011 Acknowledgments: This work was supported in part by the U.S. Department of Energy (DoE) under grants DE-AC02-09CH11466 and DE-SC0014210. This work has been carried out within the framework of the EUROfusion Consortium and has received funding from the Euratom research and training programme 2014-2018 and 2019-2020 under grant agreement No 633053. The views and opinions expressed herein do not necessarily reflect those of the European Commission.

An imidazole-functionalised cage is synthesised that can coordinate to Cu(i). X-ray analysis reveals a T-shaped coordination of copper by the imidazole ligands reminiscent of the coordination geometry found in enzymatic active sites. This cage complex can catalyse the oxidation of benzylic alcohols to benzaldehydes utilizing oxygen as the terminal oxidant. peerReviewed

The control of rotational transform in Wendelstein 7-X (W7-X) is key to both the island divertor operation and safety of plasma facing components. The island divenor concept in W7-X relies on an edge flux surface with rotational transform of t = 1 resonating with an intrinsic n/m = 5/5 resonance to form a five lobed island chain. This island chain intersects with divertor plates to give rise to the island divertor. Changes in the relative position of the rational surface and the divertor plates can result in changes in divenor performance, thus the control of the rotational transform is essential to operation of the W7-X device. During the first divertor campaign electromagnetic loads resulted in elastic deformations of the shaped modular stellarator coils. Such deformations made these coils more planar, reducing the vacuum rotational transform, subsequently shifting the t = 1 resonance outward. Unintended plasma wall interactions provided the first clear evidence of this effect during plasma operation. Flux surface measurements were utilized to estimate the correct level of current in the planar coils for correction of t, and found to be around similar to-100 A. Scans the planar coil current for iota correction were performed during plasma operation. These measurements suggest planar coil currents between -250 and similar to 0 A would place the strike lines at the designed distance from the pumping gaps. Divertor Langmuir and upstream probe measurements confirm these estimates along with measurements of divertor neutral gas pressure.

The paper presents experimental observations and simulations for the effects of toroidal plasma current on divertor power depositions on W7-X. With increasing toroidal current accompanying changes in the island geometry result in a sweep of the strike line and a redistribution of the heat flux footprints. Good agreement between experiments, which partly used electron cyclotron current drive to generate an additional toroidal current contribution, and modelling using field line tracing in vacuum magnetic fields including an ad-hoc toroidal current on the magnetic axis is found for both standard and low-iota magnetic configurations.

International audience; The Wendelstein 7-X (W7-X) optimized stellarator fusion experiment,which went into operation in 2015, has been operating since 2017 with anun-cooled modular graphite divertor. This allowed first divertor physicsstudies to be performed at pulse energies up to 80 MJ, as opposed to 4MJ in the first operation phase, where five inboard limiters wereinstalled instead of a divertor. This, and a number of other upgrades tothe device capabilities, allowed extension into regimes of higher plasmadensity, heating power, and performance overall, e.g. setting a newstellarator world record triple product. The paper focuses on the firstphysics studies of how the island divertor works. The plasma heat loadsarrive to a very high degree on the divertor plates, with only minorheat loads seen on other components, in particular baffle structuresbuilt in to aid neutral compression. The strike line shapes andlocations change significantly from one magnetic configuration toanother, in very much the same way that codes had predicted they would.Strike-line widths are as large as 10 cm, and the wetted areas alsolarge, up to about 1.5 m2, which bodes well for futureoperation phases. Peak local heat loads onto the divertor were ingeneral benign and project below the 10 MW m?2 limit of thefuture water-cooled divertor when operated with 10 MW of heating power,with the exception of low-density attached operation in the high-iotaconfiguration. The most notable result was the complete (in all 10divertor units) heat-flux detachment obtained at high-density operationin hydrogen.

The Wendelstein 7-X stellarator (W7-X), one of the largest stellarator fusion experiments, is presently being taken into operation at the Max Planck Institute for Plasma Physics in Greifswald. The main objective of the experiment is to prove the reactor relevance of the optimized stellarator concept. The W7-X experiment has a superconducting magnet system with 50 nonplanar and 20 planar coils grouped in five equal modules, which are electrically connected in 7 circuits with 10 coils of each type. The connections between the coils are made by superconducting the bus bars using the same NbTi Cable-in-Conduit Conductor as used for the superconducting coils. Particularly developed high-temperature superconducting current leads feed the current into the cryostat by bridging the temperature gradient from room temperature down to the 4-K level. Seven power supplies provide individual currents in the seven circuits. The quench detection system permanently checks the superconducting system regarding the occurrence of a quench. In case of a quench, the magnet safety system has to be activated, and a set of switches lead the current into the dump resistors. The commissioning of the magnet system was successfully performed until July 2015 with tests of the complete magnet system functionality needed for plasma operation at a magnetic field of 2.5 T.

Encapsulation of a manganese porphyrin in a self-assembled molecular cage allows catalytic epoxidation of various substrates in 1:1 water/acetonitrile mixtures. The cage acts as a phase-transfer catalyst and creates a protective environment for the catalyst improving the stability. The encapsulated catalyst also allows discrimination between styrene derivatives of various sizes. In a direct competition experiment, the selectivity of the epoxidation reaction could be inverted with respect to a benchmark catalyst.

In the version of this Article originally published, and in the associated Publisher Correction, the members of the W7-X Team were not included. All versions of the Article, and the Publisher Correction, have now been amended to include these team members.

Trioxo‐rhenium complexes are well known catalysts for the deoxydehydration (DODH) of vicinal diols (glycols). In this work, we report on the DODH of diols and biomass‐derived polyols using CpttReO3 as a new catalyst (Cptt=1,3‐di‐tert‐butylcyclopentadienyl). The DODH reaction was optimized using 2 mol % of CpttReO3 and 3‐octanol as both reductant and solvent. The CpttReO3 catalyst exhibits an excellent activity for biomass‐derived polyols. Specifically, glycerol is almost quantitatively converted to allyl alcohol and mucic acid gives 75 % of muconates at 91 % conversion. In addition, the loading of CpttReO3 can be reduced to 0.1 mol % to achieve a turn‐over number as high as 900 per Re when using glycerol as substrate. Examination of DODH reaction profiles by NMR spectroscopy indicates that catalysis is related to Cp‐ligand release, which raises questions on the nature of the actual catalyst.

Wendelstein 7-X (W7‐X) is the world’s largest superconducting nuclear fusion experiment of the optimized stellarator type. In the first Operation Phase (OP1.1) helium and hydrogen plasmas were studied in limiter configuration. The heating energy was limited to 4 MJ and the main purpose of that campaign was the integral commissioning of the machine and diagnostics, which was achieved very successfully. Already from the beginning a comprehensive set of diagnostics was available to study the plasma. On the path towards high-power, high-performance plasmas, W7‐X will be stepwise upgraded from an inertially cooled (OP1.2, limited to 80 MJ) to an actively cooled island divertor (OP2, 10 MW steady-state plasma operation). The machine is prepared for OP1.2 with 10 inertially cooled divertor units, and the experimental campaign has started recently. The paper describes a subset of diagnostics which will be available for OP1.2 to study the plasma edge, divertor and scrape-off layer physics including those already available for OP1.1, plus modifications, upgrades and new systems. The focus of this summary will be on technical and engineering aspects, like feasibility and assembly but also on reliability, thermal loads and shielding against magnetic fields.

Cobalt(III)–carbene radicals, generated through metalloradical activation of salicyl N-tosylhydrazones by cobalt(II) complexes of porphyrins, readily undergo radical addition to terminal alkynes to produce salicyl-vinyl radical intermediates. Subsequent hydrogen atom transfer (HAT) from the hydroxy group of the salicyl-moiety to the vinyl-radical leads to the formation of 2H-chromenes. The Co(II)-catalyzed process can tolerate various substitution patterns and produces the corresponding 2H-chromene products in good isolated yields. EPR spectroscopy and radical-trapping experiments with TEMPO are in agreement with the proposed radical mechanism. DFT calculations reveal the formation of the salicyl-vinyl radical intermediate by a metalloradical mediated process. Unexpectedly, subsequent HAT from the hydroxy moiety to the vinyl radical leads to formation of an o-quinone methide intermediate, which dissociates spontaneously from the cobalt center and easily undergoes an endo-cyclic, sigmatropic ring-closing reaction to form the final 2H-chromene product.

A system of three coupled catalytic cycles enabling the one-pot transformation of epoxides to amines via Meinwald rearrangement, imine condensation, and imine reduction is described. This assisted tandem catalysis is catalyzed by B(C6F5)3 resulting in the first tandem Meinwald rearrangement-reductive amination protocol. The reaction proceeds in nondried solvents and yields β-functionalized amines. In particular, β-diarylamines are obtained in high yields.

Wendelstein 7-X, a superconducting optimized stellarator built in Greifswald/Germany, started its first plasmas with the last closed flux surface (LCFS) defined by 5 uncooled graphite limiters in December 2015. At the end of the 10 weeks long experimental campaign (OP1.1) more than 20 independent diagnostic systems were in operation, allowing detailed studies of many interesting plasma phenomena. For example, fast neutral gas manometers supported by video cameras (including one fast-frame camera with frame rates of tens of kHz) as well as visible cameras with different interference filters, with field of views covering all ten half-modules of the stellarator, discovered a MARFE-like radiation zone on the inboard side of machine module 4. This structure is presumably triggered by an inadvertent plasma-wall interaction in module 4 resulting in a high impurity influx that terminates some discharges by radiation cooling. The main plasma parameters achieved in OP1.1 exceeded predicted values in discharges of a length reaching 6 s. Although OP1.1 is characterized by short pulses, many of the diagnostics are already designed for quasi-steady state operation of 30 min discharges heated at 10 MW of ECRH. An overview of diagnostic performance for OP1.1 is given, including some highlights from the physics campaigns.

Molecular flasks are compounds that are able to mediate or catalyze chemical transformations inside their cavities. The development of such compounds is often inspired by nature. Enzymes, nature’s catalysts, are able to convert a certain substrate with very high turnover number and selectivity. In addition to their very high chemo-, regio-, and stereoselectivity, enzymes are also able to distinguish their substrates on the basis of size, resulting in size selectivity. To date, many synthetic materials such as metal–organic frameworks are used to accomplish size-selective transformations. However, also the number of molecular flasks known to mediate or catalyze size-selective transformations is increasing. In this perspective an overview on classic and the most recent examples of size-selective molecular flasks is given. In addition, an outlook on promising developments in cavity chemistry that may lead to the development of additional size-selective molecular flasks is given.

Classical particle drifts are known to have substantial impacts on fluxes of particles and heat through the edge plasmas in both tokamaks and stellarators. Here we present results from the first dedicated investigation of drift effects in the W7-X stellarator. By comparing similar plasma discharges conducted with a forward- and reverse-directed magnetic field, the impacts of drifts could be isolated through the observation of up-down asymmetries in flux profiles on the divertor targets. In low-density plasmas, the radial locations of the strike lines (i.e. peaks in the target heat flux profiles) exhibited discrepancies of up to 3 cm that reversed upon magnetic field reversal. In addition, asymmetric heat loads were observed in regions of the target that are shadowed by other targets from parallel flux from the core plasma. A comparison of these asymmetric features with the footprints of key topological regions of the edge magnetic field on the divertor suggests that the main driver of the asymmetries at low density is poloidal E × B drift due to radial electric fields in the scrape-off layer and private flux region. In higher-density plasmas, upper and lower targets collected non-ambipolar currents with opposite signs that also inverted upon field reversal. Overall, in these experiments, almost all up-down asymmetry could be attributed to the field reversal and, therefore, field-dependent drifts.

Radiative power exhaust by impurity seeding was demonstrated for the first time in island divertor configurations at the stellarator Wendelstein 7-X. Feasibility of stable plasma operation was shown during seeding with both neon (Ne) and nitrogen (N2). High radiative power losses (>=80%) were found to reduce the divertor heat loads globally by 2/3 with both seeding gases injected at a single toroidal location into one of five magnetic islands. Heat flux detachment was achieved for the price of a loss of (>=-15%) in the stored energy. Ne seeding allows for sustained enhancement of edge radiation with a very slow decay of line emission of several tens of seconds after the end of the injection indicating a high recycling of this noble gas at the carbon main plasma facing components. In N2 seeded discharges it is shown that a response of line emission and plasma parameters is in correlation to the puff duration which indicates a higher level of absorption of this seeding gas in the wall. Continuous N2 seeding results in global cooling of the scrape-off layer (SOL) and decay of radiation over several seconds after the injection. Damping of counter-streaming SOL flows, and divertor particle fluxes induced by Ne and N2 seeding have been measured and provide evidence for a reduction of the convective part of the divertor heat fluxes. Losses in density in response to seeding can be compensated by feedback controlled divertor fueling. The controlled reduction of heat fluxes within this complex 3D edge island geometry is a very promising finding concerning detachment control in a future all-metal divertor.

The synthesis of a new, cubic M8L6 cage is described. This new assembly was characterised by using NMR spectroscopy, DOSY, TGA, MS, and molecular modelling techniques. Interestingly, the enlarged cavity size of this new supramolecular assembly allows the selective encapsulation of tetra(4-pyridyl)metalloporphyrins (M(II)(TPyP), M = Zn, Co). The obtained encapsulated cobalt-porphyrin embedded in the cubic zinc-porphyrin assembly is the first example of a catalytically active encapsulated transition-metal complex in a cubic M8L6 cage. The substrate accessibility of this system was demonstrated through radical-trapping experiments, and its catalytic activity was demonstrated in two different radical-type transformations. The reactivity of the encapsulated Co(II)(TPyP) complex is significantly increased compared to free Co(II)(TPyP) and other cobalt-porphyrin complexes. The reactions catalysed by this system are the first examples of cobalt-porphyrin-catalysed radical-type transformations involving diazo compounds which occur inside a supramolecular cage.

Error fields have been detected and quantified using the flux surface mapping diagnostic system on Wendelstein 7-X (W7-X). A low-field ‘ ι = 1 / 2 ’ magnetic configuration ( ι = ι / 2 π ), sensitive to error fields, was developed in order to detect their presence using the flux surface mapping diagnostic. In this configuration, a vacuum flux surface with rotational transform of n/m = 1/2 is created at the mid-radius of the vacuum flux surfaces. If no error fields are present a vanishingly small n/m = 5/10 island chain should be present. Modeling indicates that if an n = 1 perturbing field is applied by the trim coils, a large n/m = 1/2 island chain will be opened. This island chain is used to create a perturbation large enough to be imaged by the diagnostic. Phase and amplitude scans of the applied field allow the measurement of a small ∼ 0.04 m intrinsic island chain with a 130 ° phase relative to the first module of the W7-X experiment. These error fields are determined to be small and easily correctable by the trim coil system.