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).

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.

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.

The origin of biomolecular homochirality continues to be one of the most fascinating aspects of prebiotic chemistry. Various amplification strategies for chiral compounds to enhance a small chiral preference have been reported, but none of these involves phosphorylation, one of nature's essential chemical reactions. Here we present a simple and robust concept of phosphorylation-based chiral amplification of amines and amino acids in water. By exploiting the difference in solubility of a racemic phosphoramidate and its enantiopure form, we achieved enantioenrichment in solution. Starting with near racemic, phenylethylamine-based phosphoramidates, ee's of up to 95 % are reached in a single amplification step. Particularly noteworthy is the enantioenrichment of phosphorylated amino acids and their derivatives, which might point to a potential role of phosphorus en-route to prebiotic homochirality.

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 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.

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.

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.

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.

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 (ΔO) 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 T1/2 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 π-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 π-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 σ- and π-bonding.

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 Au-I catalyst, the diazonium salt undergoes electrophilic deauration of a vinyl Au-I intermediate and provides access to substituted azobenzofurans. If the reaction mixture is irradiated with blue LED light, C-C bond formation due to N-2-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 Au-I intermediate is capable of producing the observed products under photolytic and thermal conditions. The finding that a vinyl Au-I 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 Au-I intermediate and the diazonium salt.

A reversible semantics enables to undo computation steps. Reversing message-passing, concurrent programs is a challenging and delicate task; one typically aims at causally consistent reversible semantics. Prior work has addressed this challenge in the context of a process model of multiparty protocols (or choreographies). In this paper, we describe a Haskell implementation of this reversible operational semantics. We exploit algebraic data types to faithfully represent three core ingredients: a process calculus, multiparty session types, and forward and backward reduction semantics. Our implementation bears witness to the convenience of pure functional programming for implementing reversible languages.

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.