Activation of alkyl hydroperoxides by manganese complexes of tmtacn for initiation of radical polymerisation of alkenes.

The activation of alkyl hydroperoxides to generate radicals is a key step in the initiation of radical polymerisations in many industrial applications, not least protective coatings. Cobalt soaps (Co(ii) alkyl carboxylates) are highly effective catalysts under ambient conditions but viable alternatives based on less scarce catalysts are desirable, with especially iron and manganese catalysts showing potential. Manganese complexes of the ligand N,N',N″-trimethyl-1,4,7-triazacyclononane (tmtacn) are long established as catalysts for organic oxidations with H2O2, however their reactivity with alkyl hydroperoxides is less studied especially in apolar solvents. Here we show that this family of complexes can be employed as catalysts for the decomposition of alkyl hydroperoxides in apolar solvents such as styrene/methyl methacrylate mixtures and resins based on styrene/bisphenol-A based diglycidyl ether bismethacrylate (BADGE-MA). The progress of alkene polymerisation in crosslinking resins is followed by Raman spectroscopy to establish its dependence on the oxidation state of the manganese catalyst used, as gelation time and onset of autoacceleration are of particular interest for many applications. We show, through reaction progress monitoring with UV/vis absorption and Raman spectroscopy, that the stability of the manganese complexes in the resin mixtures has a substantial effect on curing progress and that the oxidation state of the resting state of the catalyst is most likely Mn(ii), in contrast to reactions with H2O2 as oxidant in which the oxidation state of the resting state of catalyst is Mn(iii). Manganese complexes of tmtacn are shown to be capable initiators of alkene radical polymerisations, and their rich coordination and redox chemistry means that resin curing kinetics can potentially be tuned more readily than with cobalt alkyl carboxylates.

Excited State Dynamics in Unidirectional Photochemical Molecular Motors.

Unidirectional photochemically driven molecular motors (PMMs) convert the energy of absorbed light into continuous rotational motion. As such they are key components in the design of molecular machines. The prototypical and most widely employed class of PMMs is the overcrowded alkenes, where rotational motion is driven by successive photoisomerization and thermal helix inversion steps. The efficiency of such PMMs depends upon the speed of rotation, determined by the rate of ground state thermal helix inversion, and the quantum yield of photoisomerization, which is dependent on the excited state energy landscape. The former has been optimized by synthetic modification across three generations of overcrowded alkene PMMs. These improvements have often been at the expense of photoisomerization yield, where there remains room for improvement. In this perspective we review the application of ultrafast spectroscopy to characterize the excited state dynamics in PMMs. These measurements lead to a general mechanism for all generations of PMMs, involving subpicosecond decay of a Franck-Condon excited state to populate a dark excited state which decays within picoseconds via conical intersections with the electronic ground state. The model is discussed in the context of excited state dynamics calculations. Studies of PMM photochemical dynamics as a function of solvent suggest exploitation of intramolecular charge transfer and solvent polarity as a route to controlling photoisomerization yield. A test of these ideas for a first generation motor reveals a high degree of solvent control over isomerization yield. These results suggest a pathway to fine control over the performance of future PMMs.

Formylation boosts the performance of light-driven overcrowded alkene-derived rotary molecular motors.

Artificial molecular motors and machines constitute a critical element in the transition from individual molecular motion to the creation of collective dynamic molecular systems and responsive materials. The design of artificial light-driven molecular motors operating with high efficiency and selectivity constitutes an ongoing fundamental challenge. Here we present a highly versatile synthetic approach based on Rieche formylation that boosts the quantum yield of the forward photoisomerization reaction while reaching near-perfect selectivity in the steps involved in the unidirectional rotary cycle and drastically reducing competing photoreactions. This motor is readily accessible in its enantiopure form and operates with nearly quantitative photoconversions. It can easily be functionalized further and outperforms its direct predecessor as a reconfigurable chiral dopant in cholesteric liquid crystal materials.

Control of Photoconversion Yield in Unidirectional Photomolecular Motors by Push-Pull Substituents.

Molecular motors based on the overcrowded alkene motif convert light energy into unidirectional mechanical motion through an excited state isomerization reaction. The realization of experimental control over conversion efficiency in these molecular motors is an important goal. Here, we combine the synthesis of a novel "push-pull" overcrowded alkene motor with photophysical characterization by steady state and ultrafast time-resolved electronic spectroscopy. We show that tuning of the charge transfer character in the excited state has a dramatic effect on the photoisomerization yield, enhancing it to near unity in nonpolar solvents while largely suppressing it in polar solvents. This behavior is explained through reference to solvent- and substituent-dependent potential energy surfaces and their effect on conical intersections to the ground state. These observations offer new routes to the fine control of motor efficiency and introduce additional degrees of freedom in the synthesis and exploitation of light-driven molecular motors.

Selective Analysis of Redox Processes at the Electrode Interface with Time-Resolved Raman Spectroscopy.

Electrochemistry and electrochemical reactions are increasingly important in the transition to a sustainable chemical industry. The electron transfer that drives such reactions takes place within nanometers of the electrode surface, and follow-up chemical reactions take place within the diffusion layer. Hence, understanding electrochemical reactions requires time-, potential-, and spatially resolved analysis. The confocal nature of Raman spectroscopy provides high spatial resolution, in addition to detailed information on molecular structure. The intrinsic weakness of nonresonant Raman scattering, however, is not sensitive enough for relatively minor changes to the solution resulting from reactions at the electrode interface. Indeed, the limit of detection is typically well above the concentrations used in electrochemical studies. Here, we show that surface-enhanced Raman scattering (SERS) and resonance Raman (rR) spectroscopy allow for spatially and time-resolved analysis of solution composition at (<1-2 nm) and near (within 5 µm) the electrode surface, respectively, in a selective manner for species present at low (<1 mM) concentrations. We show changes in concentration of species at the electrode surface, without the need for labels, specific adsorption, or resonance enhancement, using a SERS-active gold electrode prepared readily by electrochemical surface roughening. A combination of smooth and roughened gold electrodes is used to distinguish between surface and resonance enhancement using the well-known redox couples ferrocene and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS). We discuss the impact of specific adsorption on the spectral analysis with the ruthenium(II) polypyridyl complex, [Ru(bpy)3]2+. The dual function of the electrode (surface enhancement and electron transfer) in the analysis of solution processes is demonstrated with the reversible oxidation of TMA (4,N,N-trimethylaniline), where transient soluble species are identified in real time, with rapid spectral acquisition, making use of localized enhancement. We anticipate that this approach will find use in elucidating electro(catalytic) reactions at electrode interfaces.

Formation of substituted dioxanes in the oxidation of gum arabic with periodate.

Renewable polysaccharide feedstocks are of interest in bio-based food packaging, coatings and hydrogels. Their physical properties often need to be tuned by chemical modification, e.g. by oxidation using periodate, to introduce carboxylic acid, ketone or aldehyde functional groups. The reproducibility required for application on an industrial scale, however, is challenged by uncertainty about the composition of product mixtures obtained and of the precise structural changes that the reaction with periodate induces. Here, we show that despite the structural diversity of gum arabic, primarily rhamnose and arabinose subunits undergo oxidation, whereas (in-chain) galacturonic acids are unreactive towards periodate. Using model sugars, we show that periodate preferentially oxidises the anti 1,2-diols in the rhamnopyranoside monosaccharides present as terminal groups in the biopolymer. While formally oxidation of vicinal diols results in the formation of two aldehyde groups, only traces of aldehydes are observed in solution, with the main final products obtained being substituted dioxanes, both in solution and in the solid state. The substituted dioxanes form most likely by the intramolecular reaction of one aldehyde with a nearby hydroxyl group, followed by hydration of the remaining aldehyde to form a geminal diol. The absence of significant amounts of aldehyde functional groups in the modified polymer impacts crosslinking strategies currently attempted in the preparation of renewable polysaccharide-based materials.

A Common Active Intermediate in the Oxidation of Alkenes, Alcohols and Alkanes with H2O2 and a Mn(II)/Pyridin-2-Carboxylato Catalyst.

The mechanism and the reactive species involved in the oxidation of alkenes, and alcohols with H2O2, catalysed by an in situ prepared mixture of a MnII salt, pyridine-2-carboxylic acid and a ketone is elucidated using substrate competition experiments, kinetic isotope effect (KIE) measurements, and atom tracking with 18O labelling. The data indicate that a single reactive species engages in the oxidation of both alkenes and alcohols. The primary KIE in the oxidation of benzyl alcohols is ca. 3.5 and shows the reactive species to be selective despite a zero order dependence on substrate concentration, and the high turnover frequencies (up to 30 s-1) observed. Selective 18O labelling identifies the origin of the oxygen atoms transferred to the substrate during oxidation, and is consistent with a highly reactive, e. g., [MnV(O)(OH)] or [MnV(O)2], species rather than an alkylperoxy or hydroperoxy species.

Ultrafast motion in a third generation photomolecular motor.

Controlling molecular translation at the nanoscale is a key objective for development of synthetic molecular machines. Recently developed third generation photochemically driven molecular motors (3GMs), comprising pairs of overcrowded alkenes capable of cooperative unidirectional rotation offer the possibility of converting light energy into translational motion. Further development of 3GMs demands detailed understanding of their excited state dynamics. Here we use time-resolved absorption and emission to track population and coherence dynamics in a 3GM. Femtosecond stimulated Raman reveals real-time structural dynamics as the excited state evolves from a Franck-Condon bright-state through weakly-emissive dark-state to the metastable product, yielding new insight into the reaction coordinate. Solvent polarity modifies the photoconversion efficiency suggesting charge transfer character in the dark-state. The enhanced quantum yield correlates with suppression of a low-frequency flapping motion in the excited state. This detailed characterization facilitates development of 3GMs, suggesting exploitation of medium and substituent effects to modulate motor efficiency.

Light-driven molecular motors embedded in covalent organic frameworks.

The incorporation of molecular machines into the backbone of porous framework structures will facilitate nano actuation, enhanced molecular transport, and other out-of-equilibrium host-guest phenomena in well-defined 3D solid materials. In this work, we detail the synthesis of a diamine-based light-driven molecular motor and its incorporation into a series of imine-based polymers and covalent organic frameworks (COF). We study structural and dynamic properties of the molecular building blocks and derived self-assembled solids with a series of spectroscopic, diffraction, and theoretical methods. Using an acid-catalyzed synthesis approach, we are able to obtain the first crystalline 2D COF with stacked hexagonal layers that contains 20 mol% molecular motors. The COF features a specific pore volume and surface area of up to 0.45 cm3 g-1 and 604 m2 g-1, respectively. Given the molecular structure and bulkiness of the diamine motor, we study the supramolecular assembly of the COF layers and detail stacking disorders between adjacent layers. We finally probe the motor dynamics with in situ spectroscopic techniques revealing current limitations in the analysis of these new materials and derive important analysis and design criteria as well as synthetic access to new generations of motorized porous framework materials.

pH-Induced Changes in the SERS Spectrum of Thiophenol at Gold Electrodes during Cyclic Voltammetry.

Thiophenol is a model compound used in the study of self-assembly of arylthiols on gold surfaces. In particular, changes in the surface-enhanced Raman scattering (SERS) spectra of these self-assembled monolayers (SAMs) with a change of conditions have been ascribed to, for example, differences in orientation with respect to the surface, protonation state, and electrode potential. Here, we show that potential-induced changes in the SERS spectra of SAMs of thiophenol on electrochemically roughened gold surfaces can be due to local pH changes at the electrode. The changes observed during the potential step and cyclic voltammetry experiments are identical to those induced by acid-base switching experiments in a protic solvent. The data indicate that the potential-dependent spectral changes, assigned earlier to changes in molecular orientation with respect to the surface, can be ascribed to changes in the pH locally at the electrode. The pH at the electrode can change as much as several pH units during electrochemical measurements that reach positive potentials where oxidation of adventitious water can occur. Furthermore, once perturbed by applying positive potentials, the pH at the electrode takes considerable time to recover to that of the bulk solution. It is noted that the changes in pH even during cyclic voltammetry in organic solvents can be equivalent to the addition of strong acids, such as CF3SO3H, and such effects should be considered in the study of the redox chemistry of pH-sensitive redox systems and potential-dependent SERS in particular.

In situ EPR and Raman spectroscopy in the curing of bis-methacrylate-styrene resins.

The curing of bis-methacrylate-styrene resins initiated by the cobalt catalyzed decomposition of cumyl hydroperoxide is monitored at ambient temperatures in situ by EPR and Raman spectroscopy. EPR spectroscopy shows the appearance of organic radicals after ca. 1 h from initiation with an increase in intensity from both polystyrene and methacrylate based radical species over a further ca. 2 h period to reach a maximum spin concentration of ca. 2-3 mM. Alkene conversion to polymer was monitored by Raman spectroscopy in real time in situ with EPR spectroscopy and reveals that the appearance of the radical signals is first observed only as the conversion approaches its maximum extent (70% at room temperature), i.e., the resin reaches a glass-like state. The radicals persist for several months on standing at room temperature. Flash frozen samples (77 K) did not show EPR signals within 1 h of initiation. The nature of the radicals responsible for the EPR spectra observed were explored by DFT methods and isotope labelling experiments (D8-styrene) and correspond to radicals of both methacrylate and polystyrene. Combined temperature dependent EPR and Raman spectroscopy shows that conversion increases rapidly upon heating of a cured sample, reaching full conversion at 80 °C with initially little effect on the EPR spectrum. Over time (i.e. subsequent to reaching full conversion of alkene) there was a small but clear increase in the EPR signal due to the methacrylate based radicals and minor decrease in the signal due to the polystyrene based radicals. The appearance of the radical signals as the reaction reaches completion and their absence in samples flash frozen before polymerization has halted, indicate that the observed radicals are non-propagating. The formation of the radicals due to stress within the samples is excluded. Hence, the observed radicals are a representative of the steady state concentration of radicals present in the resin over the entire timespan of the polymerization. The data indicate that the lack of EPR signals is most likely due to experimental aspects, in particular spin saturation, rather than low steady state concentrations of propagating radicals during polymerization.

Cooperative light-induced breathing of soft porous crystals via azobenzene buckling.

Although light is a prominent stimulus for smart materials, the application of photoswitches as light-responsive triggers for phase transitions of porous materials remains poorly explored. Here we incorporate an azobenzene photoswitch in the backbone of a metal-organic framework producing light-induced structural contraction of the porous network in parallel to gas adsorption. Light-stimulation enables non-invasive spatiotemporal control over the mechanical properties of the framework, which ultimately leads to pore contraction and subsequent guest release via negative gas adsorption. The complex mechanism of light-gated breathing is established by a series of in situ diffraction and spectroscopic experiments, supported by quantum mechanical and molecular dynamic simulations. Unexpectedly, this study identifies a novel light-induced deformation mechanism of constrained azobenzene photoswitches relevant to the future design of light-responsive materials.

Photoswitchable architecture transformation of a DNA-hybrid assembly at the microscopic and macroscopic scale.

Molecular recognition-driven self-assembly employing single-stranded DNA (ssDNA) as a template is a promising approach to access complex architectures from simple building blocks. Oligonucleotide-based nanotechnology and soft-materials benefit from the high information storage density, self-correction, and memory function of DNA. Here we control these beneficial properties with light in a photoresponsive biohybrid hydrogel, adding an extra level of function to the system. An ssDNA template was combined with a complementary photo-responsive unit to reversibly switch between various functional states of the supramolecular assembly using a combination of light and heat. We studied the structural response of the hydrogel at both the microscopic and macroscopic scale using a combination of UV-vis absorption and CD spectroscopy, as well as fluorescence, transmission electron, and atomic force microscopy. The hydrogels grown from these supramolecular self-assembly systems show remarkable shape-memory properties and imprinting shape-behavior while the macroscopic shape of the materials obtained can be further manipulated by irradiation.

Photoactive Fe Catalyst for Light-Triggered Alkyd Paint Curing.

Herein, we show that the photoactive complexes [(Cp)Fe(arene)]+ (Cp = cyclopentadienyl; arene = C6H6, C6H5Me) act as latent catalysts that allow for photochemical control over the onset of alkyd paint curing, without the need for antiskinning agents such as the volatile 2-butanone oxime normally used to prevent curing during paint storage. The highly soluble neutral complexes [(Cp)Fe(Ch)] and [(Cp)Fe(Ch')] (Ch = cyclohexadienyl, Ch' = methylcyclohexadienyl) readily convert to the photoactive complexes [(Cp)Fe(arene)]+ upon oxidation in alkyd, allowing the latter to be dosed in a wide range of concentrations. Infrared and Raman studies show similar spectral changes of the alkyd paint matrix as have been observed in alkyd curing mediated by well-known, industrially applied cobalt- and manganese-based catalyst Co(neodecanoate)2 and [(Me3TACN)2Mn2(µ-OOCR)3](OOCR). The [(Cp)Fe(Ch)]/[(Cp)Fe(arene)]+ system performs equally well as these cobalt- and manganese-based catalysts in terms of drying time and outperform the manganese catalyst by showing a hardness development (increase) similar to that of the cobalt-based catalyst. Based on electron paramagnetic resonance and light-activity studies, we propose that photolysis of [(Cp)Fe(arene)]+ generates short-lived active FeII species, explaining the desired latency. The [(Cp)Fe(Ch)]/[(Cp)Fe(arene)]+ alkyd curing systems presented herein are unique examples of intrinsically latent paint curing catalysts that (1) are based on an abundant and harmless transition metal (Fe), (2) do not require any antiskinning agents, and (3) show favorable performance in terms of drying times and hardness development.

Taming Tris(bipyridine)ruthenium(II) and Its Reactions in Water by Capture/Release with Shape-Switchable Symmetry-Matched Cyclophanes.

Electron/proton transfers in water proceeding from ground/excited states are the elementary reactions of chemistry. These reactions of an iconic class of molecules─polypyridineRu(II)─are now controlled by capturing or releasing three of them with hosts that are shape-switchable. Reversible erection or collapse of the host walls allows such switchability. Some reaction rates are suppressed by factors of up to 120 by inclusive binding of the metal complexes. This puts nanometric coordination chemistry in a box that can be open or shut as necessary. Such second-sphere complexation can allow considerable control to be exerted on photocatalysis, electrocatalysis, and luminescent sensing involving polypyridineRu(II) compounds. The capturing states of hosts are symmetry-matched to guests for selective binding and display submicromolar affinities. A perching complex, which is an intermediate state between capturing and releasing states, is also demonstrated.

Single wavelength colour tuning of spiropyran and dithienylethene based photochromic coatings.

Controlling the transmission of thin films with external stimuli is an important goal in functional optical materials and devices. Tuning is especially challenging where both broad band (neutral density filtering) and spectrally varied (colour) transmission are required. The external control provided by photochemically driven switching, between transmission levels and colours, is functionally simple from a device perspective. The limits due to the spectral ranges of individual photochromic compounds can be overcome by combining several photochromes within one material or device. Here we show that a combination of photochromic molecular switches immobilised in a PMMA polymer matrix enables tuning of colour and transparency. We show that only a single excitation wavelength is required through the use of the primary inner filter effect and the layered construction of the films in which the photochromes nitrospiropyran (NSP), and nitrothiospiropyran (TSP) or 1,2-bis-terthienyl-hexafluorocyclopentene (DTE) are separated spatially. The approach taken circumvents the need to match photochemical quantum yields and thermal reactivity of the component photochromes. The photochemical switching of the films was characterised by UV/vis absorption spectroscopy and shows that switching rates and photostationary states are limited by inner filter effects rather than the intrinsic properties of photochromes, such as photochemical quantum yields and thermal stability. The photochemical behaviour and stability of the photochromes in solution and in the PMMA films were compared and the concentration range over which self-inhibition of photochemical switching occurs was established. The rate of photochemical switching and the difference in transmission between the spiropyran and merocyanine forms in solution enable prediction of the performance in the films and enable rational design of colour tuning ranges and responsivity in thin film filters.

Stereodivergent Chirality Transfer by Noncovalent Control of Disulfide Bonds.

Controlling dynamic stereochemistry is an important challenge, as it is not only inherent to protein structure and function but often governs supramolecular systems and self-assembly. Typically, disulfide bonds exhibit stereodivergent behavior in proteins; however, how chiral information is transmitted to disulfide bonds remains unclear. Here, we report that hydrogen bonds are essential in the control of disulfide chirality and enable stereodivergent chirality transfer. The formation of S-S···H-N hydrogen bonds in solution can drive conformational adaption to allow intramolecular chirality transfer, while the formation of C=O···H-N hydrogen bonds results in supramolecular chirality transfer to form antiparallel helically self-assembled solid-state architectures. The dependence on the structural information encoded in the homochiral amino acid building blocks reveals the remarkable dynamic stereochemical space accessible through noncovalent chirality transmission.

Three-State Switching of an Anthracene Extended Bis-thiaxanthylidene with a Highly Stable Diradical State.

A multistable molecular switching system based on an anthracene-extended bis-thiaxanthylidene with three individually addressable states that can be interconverted by electrochemical, thermal, and photochemical reactions is reported. Besides reversible switching between an open-shell diradical- and a closed-shell electronic configuration, our findings include a third dicationic state and control by multiple actuators. This dicationic state with an orthogonal conformation can be switched electrochemically with the neutral open-shell triplet state with orthogonal conformation, which was characterized by EPR. The remarkably stable diradical shows kinetic stability as a result of a significant activation barrier for isomerization to a more stable neutral closed-shell folded geometry. We ascribe this activation barrier of ΔG⧧(293 K) = 25.7 kcal mol-1 to steric hindrance in the fjord region of the overcrowded alkene structure. The folded closed-shell state can be converted back to the diradical state by irradiation with 385 nm. The folded state can also be oxidized to the dicationic state. These types of molecules with multiple switchable states and in particular stable diradicals show great potential in the design of new functional materials such as memory devices, logic gates, and OFETs.

Iron Tetrasulfonatophthalocyanine-Catalyzed Starch Oxidation Using H2O2: Interplay between Catalyst Activity, Selectivity, and Stability.

Oxidized starch can be efficiently prepared using H2O2 as an oxidant and iron(III) tetrasulfophthalocyanine (FePcS) as a catalyst, with properties in the same range as those for commercial oxidized starches prepared using NaOCl. Herein, we performed an in-depth study on the oxidation of potato starch focusing on the mode of operation of this green catalytic system and its fate as the reaction progresses. At optimum batch reaction conditions (H2O2/FePcS molar ratio of 6000, 50 °C, and pH 10), a high product yield (91 wt %) was obtained with substantial degrees of substitution (DSCOOH of 1.4 and DSCO of 4.1 per 100 AGU) and significantly reduced viscosity (197 mPa·s) by dosing H2O2. Model compound studies showed limited activity of the catalyst for C6 oxidation, indicating that carboxylic acid incorporation likely results from C-C bond cleavage events. The influence of the process conditions on the stability of the FePcS catalyst was studied using UV-vis and Raman spectroscopic techniques, revealing that both increased H2O2 concentration and temperature promote the irreversible degradation of the FePcS catalyst at high pH. The rate and extent of FePcS degradation were found to strongly depend on the initial H2O2 concentration where also the rapid decomposition of H2O2 by FePcS occurs. These results explain why the slow addition of H2O2 in combination with low FePcS catalyst concentration is beneficial for the efficient application in starch oxidation.

Isolation of a Ru(IV) side-on peroxo intermediate in the water oxidation reaction.

The electrons that nature uses to reduce CO2 during photosynthesis come from water oxidation at the oxygen-evolving complex of photosystem II. Molecular catalysts have served as models to understand its mechanism, in particular the O-O bond-forming reaction, which is still not fully understood. Here we report a Ru(IV) side-on peroxo complex that serves as a 'missing link' for the species that form after the rate-determining O-O bond-forming step. The Ru(IV) side-on peroxo complex (η2-1iv-OO) is generated from the isolated Ru(IV) oxo complex (1iv=O) in the presence of an excess of oxidant. The oxidation (IV) and spin state (singlet) of η2-1iv-OO were determined by a combination of experimental and theoretical studies. 18O- and 2H-labelling studies evidence the direct evolution of O2 through the nucleophilic attack of a H2O molecule on the highly electrophilic metal-oxo species via the formation of η2-1iv-OO. These studies demonstrate water nucleophilic attack as a viable mechanism for O-O bond formation, as previously proposed based on indirect evidence.