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Redox flow batteries based on organic electrolytes are promising energy storage devices, but stable long-term cycling is often difficult to achieve. Bipolar organic charge-storage materials allow the construction of symmetrical flow batteries (i. e., with identical electrolyte composition on both sides), which is a strategy to mitigate crossover-induced degradation. One such class of bipolar compounds are verdazyl radicals, but little is known on their stability/reactivity either as the neutral radical, or in the charged states. Here, we study the chemical properties of a Kuhn-type verdazyl radical (1) and the oxidized/reduced form (1+/−). Chemical synthesis of the three redox-states provides spectroscopic characterization data, which are used as reference for evaluating the composition of the electrolyte solutions of an H-cell battery during/after cycling. Our data suggest that, rather than the charged states, the decomposition of the parent verdazyl radical is responsible for capacity fade. Kinetic experiments and DFT calculations provide insight in the decomposition mechanism, which is shown to occur by bimolecular disproportionation to form two closed-shell products (leuco-verdazyl 1H and triazole derivative 2).

Chiral optical switches, which use light to control chirality in a reversible manner, offer unique properties and fascinating prospects in the areas of molecular switching and responsive systems, new photochromic materials and molecular data processing and storage. Herein, we report visible light responsive chiroptical switches based on tetrahedral boron coordination towards an easily accessible hydrazone ligand and optically pure BINOL. Upon instalment of a non-planar dibenzo[a,d]-cycloheptene moiety in the hydrazone ligand's lower half, the enantiopure boron complex shows major chiroptical changes in the CD read-out after visible light irradiation. The thermal isomerization barrier in these chiroptical switching systems showed to be easily adjustable by the introduction of substituents onto the olefinic bond of the cycloheptene ring, giving profound control over their thermal stability. The control over their thermal stability in combination with excellent reversibility, photochemical properties and overall robustness of the complexes makes these BINOL-derived chiroptical switches attractive candidates for usage in advanced applications, e.g. photonic materials and nanotechnology.

We report the synthesis and crystallographic characterization of a novel Au(III)−OH complex featuring a N^N^N-pincer ligand. Reactivity studies towards oxygen atom transfer (OAT), a type of reactivity previously reported for a Au(III)−OH complex, indicate that this complex provides both a sterically encumbered Au atom and a sterically poorly accessible OH group leading to no reactivity with a series of phosphines. The steric encumbrance sets this example apart from the known examples of Au(III)−OH (pincer) complexes, which commonly feature planar ligands that provide little control over steric accessibility of the Au and O atoms in these complexes. Implications for the mechanism of OAT from Au−OH complexes are briefly discussed.

A series of heteroleptic three-coordinate mono(formazanate)zinc methyl complexes were synthesized, and the influence of the ligand on the structure as well as redox and optical properties of these complexes was investigated. The heteroleptic mono(formazanate)zinc methyl complexes were found to show ligand redistribution in solution, reminiscent of the Schlenk equilibrium, to generate an equilibrium mixture containing the corresponding homoleptic complexes as well. Monitoring the approach to equilibrium by NMR spectroscopy in benzene-d(6) allowed determination of the forward and backward rate constants. A correlation was found between the steric environment around the zinc center and equilibrium concentration of (formazanate)zinc methyl compounds, whereas the kinetics for approach to equilibrium are also dependent on the electronic properties.

The transition between spin states in d-block metal complexes has important ramifications for their structure and reactivity, with applications ranging from information storage materials to understanding catalytic activity of metalloenzymes. Tuning the ligand field (Delta(O)) by steric and/or electronic effects has provided spin-crossover compounds for several transition metals in the periodic table, but this has mostly been limited to coordinatively saturated metal centers in octahedral ligand environments. Spin-crossover complexes with low coordination numbers are much rarer. Here we report a series of four-coordinate, (pseudo)tetrahedral Fe(II) complexes with formazanate ligands and demonstrate how electronic substituent effects can be used to modulate the thermally induced transition between S = 0 and S = 2 spin states in solution. All six compounds undergo spin-crossover in solution with T-1/2 above room temperature (300-368 K). While structural analysis by X-ray crystallography shows that the majority of these compounds are low-spin in the solid state (and remain unchanged upon heating), we find that packing effects can override this preference and give rise to either rigorously high-spin (6) or gradual spin-crossover behavior (5) also in the solid state. Density functional theory calculations are used to delineate the empirical trends in solution spin-crossover thermodynamics. In all cases, the stabilization of the low-spin state is due to the pi-acceptor properties of the formazanate ligand, resulting in an "inverted" ligand field, with an approximate "two-over-three" splitting of the d-orbitals and a high degree of metal-ligand covalency due to metal -> ligand pi-backdonation. The computational data indicate that the electronic nature of the para-substituent has a different influence depending on whether it is present at the C-Ar or N-Ar rings, which is ascribed to the opposing effect on metal-ligand sigma- and pi-bonding.

Redox-switching of a formazanate zinc catalyst in ring-opening polymerization (ROP) of lactide is described. Using a redox-active ligand bound to an inert metal ion (Zn2+) allows modulation of the catalytic activity by reversible reduction/oxidation chemistry at a purely organic fragment. A combination of kinetic and spectroscopic studies, together with mass spectrometry of the catalysis mixture, provides insight in the nature of the active species and the initiation of lactide ring-opening polymerization. The mechanistic data highlight the key role of the redox-active ligand and provide a rationale for the formation of cyclic polymer.

Here we report that chiral Mn(I) complexes are capable of H-P bond activation. This activation mode enables a general method for the hydrophosphination of internal and terminal α,β-unsaturated nitriles. Metal-ligand cooperation, a strategy previously not considered for catalytic H-P bond activation, is at the base of the mechanistic action of the Mn(I)-based catalyst. Our computational studies support a stepwise mechanism for the hydrophosphination and provide insight into the origin of the enantioselectivity.

In a systematic study of the Au‐catalyzed reaction of o‐alkynylphenols with aryldiazonium salts, we find that essentially the same reaction conditions lead to a change in mechanism when a light source is applied. If the reaction is carried out at room temperature using a AuI catalyst, the diazonium salt undergoes electrophilic deauration of a vinyl AuI intermediate and provides access to substituted azobenzofurans. If the reaction mixture is irradiated with blue LED light, C−C bond formation due to N2‐extrusion from the diazonium salt is realized selectively, using the same starting materials without the need for an additional photo(redox) catalyst under aerobic conditions. We report a series of experiments demonstrating that the same vinyl AuI intermediate is capable of producing the observed products under photolytic and thermal conditions. The finding that a vinyl AuI complex can directly, without the need for an additional photo(redox) catalyst, result in C−C bond formation under photolytic conditions is contrary to the proposed mechanistic pathways suggested in the literature till date and highlights that the role of oxidation state changes in photoredox catalysis involving Au is thus far only poorly understood and may hold surprises for the future. Computational results indicate that photochemical activation can occur directly from a donor–acceptor complex formed between the vinyl AuI intermediate and the diazonium salt., The Au‐catalyzed reaction of o‐alkynylphenols with aryldiazonium salts undergoes a change in mechanism when a light source is applied. If the reaction is carried out at room temperature using a AuI catalyst, the diazonium salt undergoes electrophilic deauration of a vinyl AuI intermediate generating substituted azobenzofurans. If the reaction mixture is irradiated with blue LED light, C−C bond formation due to N2‐extrusion from the diazonium salt is observed.

Monoalkyltin(iv) complexes are well-known catalysts for esterification reactions and polyester formation, yet the mode of operation of these Lewis acidic complexes is still unknown. Here, we report on mechanistic studies of n-butylstannoic acid in stoichiometric and catalytic reactions, analyzed by NMR, IR and MS techniques. While the chemistry of n-butyltin(iv) carboxylates is dominated by formation of multinuclear tin assemblies, we found that under catalytically relevant conditions only monomeric n-BuSn(OAc)3 and dimeric (n-BuSnOAc2OEt)2 are present. Density functional theory (DFT) calculations provide support for a mononuclear mechanism, where n-BuSn(OAc)3 and dimeric (n-BuSnOAc2OEt)2 are regarded as off-cycle species, and suggest that carbon–oxygen bond breaking is the rate-determining step., Monoalkyltin-catalyzed esterification was studied under industrially relevant catalytic conditions and was found to have a monomeric active species, with both a monomeric and a dimeric resting state.

Bis(formazanate)iron(II) complexes undergo a thermally induced S = 0 to S = 2 spin transition in solution. Here we present a study of how steric effects and π-stacking interactions between the triarylformazanate ligands affect the spin-crossover behavior, in addition to electronic substituent effects. Moreover, the effect of increasing the denticity of the formazanate ligands is explored by including additional OMe donors in the ligand (7). In total, six new compounds (2–7) have been synthesized and characterized, both in solution and in the solid state, via spectroscopic, magnetic, and structural analyses. The series spans a broad range of spin-crossover temperatures (T1/2) for the LS ⇌ HS equilibrium in solution, with the exception of compound 6 which remains high-spin (S = 2) down to 210 K. In the solid state, 6 was shown to exist in two distinct forms: a tetrahedral high-spin complex (6a, S = 2) and a rare square-planar structure with an intermediate-spin state (6b, S = 1). SQUID measurements, 57Fe Mössbauer spectroscopy, and differential scanning calorimetry indicate that in the solid state the square-planar form 6b undergoes an incomplete spin-change-coupled isomerization to tetrahedral 6a. The complex that contains additional OMe donors (7) results in a six-coordinate (NNO)2Fe coordination geometry, which shifts the spin-crossover to significantly higher temperatures (T1/2 = 444 K). The available experimental and computational data for 7 suggest that the Fe···OMe interaction is retained upon spin-crossover. Despite the difference in coordination environment, the weak OMe donors do not significantly alter the electronic structure or ligand-field splitting, and the occurrence of spin-crossover (similar to the compounds lacking the OMe groups) originates from a large degree of metal–ligand π-covalency., A series of Fe(II) complexes with formazanate ligands are reported, and ligand substituent effects on structure and spin-crossover properties are examined. These ligand modifications allow isolation of compounds with tetrahedral geometries in both low- and high-spin ground states as well as an intermediate-spin square-planar complex. Steric properties, π-stacking interactions, and additional donor substituents lead to a wide range of spin-crossover temperatures (T1/2) in this class of compounds.

Peatlands offer a series of ecosystem services including carbon storage, biomass production, and climate regulation. Climate change and rapid land use change are degrading peatlands, liberating their stored carbon (C) into the atmosphere. To conserve peatlands and help in realising the Paris Agreement, we need to understand their extent, status, and C stocks. However, current peatland knowledge is vague—estimates of global peatland extent ranges from 1 to 4.6 million km2, and C stock estimates vary between 113 and 612 Pg (or billion tonne C). This uncertainty mostly stems from the coarse spatial scale of global soil maps. In addition, most global peatland estimates are based on rough country inventories and reports that use outdated data. This review shows that digital mapping using field observations combined with remotely-sensed images and statistical models is an avenue to more accurately map peatlands and decrease this knowledge gap. We describe peat mapping experiences from 12 countries or regions and review 90 recent studies on peatland mapping. We found that interest in mapping peat information derived from satellite imageries and other digital mapping technologies is growing. Many studies have delineated peat extent using land cover from remote sensing, ecology, and environmental field studies, but rarely perform validation, and calculating the uncertainty of prediction is rare. This paper then reviews various proximal and remote sensing techniques that can be used to map peatlands. These include geophysical measurements (electromagnetic induction, resistivity measurement, and gamma radiometrics), radar sensing (SRTM, SAR), and optical images (Visible and Infrared). Peatland is better mapped when using more than one covariate, such as optical and radar products using nonlinear machine learning algorithms. The proliferation of satellite data available in an open-access format, availability of machine learning algorithms in an open-source computing environment, and high-performance computing facilities could enhance the way peatlands are mapped. Digital soil mapping allows us to map peat in a cost-effective, objective, and accurate manner. Securing peatlands for the future, and abating their contribution to atmospheric C levels, means digitally mapping them now.

Palladium(ii) complexes with a bidentate, anionic formazanate ligand are described. Attempts to prepare mono(formazanate) palladium alkyl complexes often leads to the homoleptic bis(formazanate) complex, which shows rich electrochemistry due to the redox-active nature of the ligands. Performing salt metathesis between the precursor [Pd(COD)(CH3)Cl] and the potassium salt of the ligand in the presence of tetrabutylammonium chloride yields a square planar mono(formazanate) palladate complex through coordination of chloride anion. Ligand exchange allows binding of unsaturated molecules and evaluation of the reactivity of the Pd-CH3 fragment. Using this approach, insertion reactions of CO, isocyanide and methyl acrylate into the Pd-CH3 bond are demonstrated.

De bodemkaart onderscheidt allerlei bodemtypen met veenlagen ondiep in het profiel. Door oxidatie en klink neemt de veendikte geleidelijk af. Voor het beheer van veengebieden is het van belang om inzicht te hebben in de veendiktes. Dit onderzoek heeft geresulteerd in een veendiktekaart voor het westelijk veengebied in Waterschap Drents Overijsselse Delta en een geactualiseerde bodemkaart, schaal 1 : 50 000, van dit veengebied.

This study compared the efficiency of geostatistical digital soil mapping (DSM) with conventional soil mapping (CSM) for updating soil class and property maps of a cultivated peatland in the Netherlands. For digital soil class mapping, the generalized linear geostatistical model was used. Digital mapping of the soil organic matter (SOM) content and peat thickness was done by universal kriging. The conventional soil class map was created by free survey, while the property maps were created with the representative profile description (RPD) and map unit means (MUM) methods. For each method, we computed the effort invested in the mapping in terms of the sampling and cost densities. The accuracies of the created soil maps were estimated from independent probability sample data. The results showed that for DSM, the cost density could be reduced by a factor of three compared with CSM without compromising accuracy. The map purity of both maps was around 55%. For conventional soil property mapping, the MUM maps were more accurate than the RPD maps. For SOM, CSM-MUM (RMSE 7.5%) performed better than DSM (RMSE 12.1%), although accuracy differences were not significant. For peat thickness, DSM (RMSE 23.3 cm) performed slightly better than CSM-MUM (RMSE 24.9 cm). Despite the differences in accuracy being small, the digital soil property maps were produced more efficiently. The cost density was a factor of 3.5 smaller. We conclude that for updating conventional soil maps in the Dutch peatlands, geostatistical DSM can be more efficient, although not necessarily more accurate, than CSM.

Voor de ontwikkeling van het Nationaal Hydrologisch Instrumentarium-waterkwaliteit is een aanpak opgesteld om de fysisch-chemische schematisering van de bodem in Nederland verder te ontwikkelen. Op korte termijn (2017-2018) is een pragmatische werkwijze nodig om de bodemchemische parameters met bijbehorende schematisering in representatieve eenheden voor de operationele toepassing voor landelijke beleidsstudies te actualiseren. Het gebruik van de huidige fysischchemische karakterisering voor de bodemkaart 1:50.000 vormt de geëigende methode. Op de langere termijn is het de wens om het Nationaal Hydrologisch Instrumentarium-waterkwaliteit ook te kunnen inzetten voor regionale toepassingen. Dit kan alleen als er een gedetailleerde geostatistisch gesimuleerde 3D-bodemkaart aan ten grondslag ligt die recht doen aan regionale variabiliteit van de bodem.

This paper presents a pedometric approach to updating the Dutch 1:50,000 national soil map for the peatlands, and illustrates this approach for a 187,525 ha area in the northern peatlands. This is the first time that digital soil mapping replaces conventional soil mapping in a nationwide, government-funded soil survey program in the Netherlands. Soil classes were updated indirectly through mapping two quantitative diagnostic soil properties: the thickness and starting depth of the peat layer. From these, five major soil groups could be constructed. Because the point data were zero-inflated, a two-step simulation approach was implemented. First, peat presence/absence indicators were simulated from probabilities of peat occurrence that were predicted with a generalized linear model. Second, conditional peat thickness values were simulated from kriging with external drift predictions. The indicator and peat thickness simulations were combined to obtain simulations of the unconditional peat thickness. A similar approach was followed for the starting depth. From the simulated soil properties, probability distributions of soil groups were derived. These groups were refined with information on (static) soil properties derived from the 1:50,000 map to obtain soil classes according to the 1:50,000 legend. The updated raster map was then incorporated in the 1:50,000 polygon map. The prediction models were calibrated with legacy point data, that were updated for peat thickness before being used, in addition to a set of newly acquired point data. The uncertainty associated to the updated peat thickness values in the legacy dataset was quantified and accounted for by the prediction models. The peat thickness map and a map with three soil orders were validated with independent probability sample data. The overall purity of the soil order map was 66% for both subareas. For subarea 1 this was a 12% purity improvement compared to the current 1:50,000 map, for subarea 2 this was 3%. For subarea 1, the mean absolute error of the predicted peat thickness was 23.5 cm, and the R2 is 0.50. For subarea 2 these accuracy measures were 30.9 cm and 0.65. We conclude that nationwide updating the 1:50,000 map with pedometric techniques is feasible. In order to increase the value and usability of the legacy point data as well as the large set of newly acquired field observations and the updated 1:50,000 map, we recommend installation of a soil monitoring network in the Dutch peatlands.