Substituent effects on first generation photochemical molecular motors probed by femtosecond stimulated Raman.

Unidirectional photochemical molecular motors can act as a power source for molecular machines. The motors operate by successive excited state isomerization and ground state helix inversion reactions, attaining unidirectionality from an interplay of steric strain and stereochemistry. Optimizing the yield of the excited state isomerization reaction is an important goal that requires detailed knowledge of excited state dynamics. Here, we investigate the effect of electron withdrawing and donating substituents on excited state structure and ultrafast dynamics in a series of newly synthesized first generation photochemical molecular motors. All substituents red-shift the absorption spectra, while some modify the Stokes shift and render the fluorescence quantum yield solvent polarity dependent. Raman spectra and density functional theory calculations reveal that the stretching mode of the C=C "axle" in the electronic ground state shows a small red-shift when conjugated with electron withdrawing substituents. Ultrafast fluorescence measurements reveal substituent and solvent polarity effects, with the excited state decay being accelerated by both polar solvent environment and electron withdrawing substituents. Excited state structural dynamics are investigated by fluorescence coherence spectroscopy and femtosecond stimulated Raman spectroscopy. The time resolved Raman measurements are shown to provide structural data specifically on the Franck-Condon excited state. The C=C localized modes have a different substituent dependence compared to the ground state, with the unsubstituted motor having the most red-shifted mode. Such measurements provide valuable new insights into pathways to optimize photochemical molecular motor performance, especially if they can be coupled with high-quality quantum molecular dynamics calculations.

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.

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.

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.

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.

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.

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.

Electrochemical Ring-Opening and -Closing of a Spiropyran.

The bistability of molecular switches is an essential characteristic in their use as functional components in molecular-based devices and machines. For photoswitches, light-driven switching between two stable states proceeds via short-lived changes of the bond order in electronically excited states. Here, bistable switching of a ditertbutyl-substituted spiropyran photoswitch is instead demonstrated by oxidation and subsequent reduction in an overall four-state cycle. The spiropyran structure chosen has reduced sensitivity to the effect of secondary electrochemical processes such as H+ production and provides transient access to a decreased thermal Z-E isomerization barrier in the one electron oxidized state, akin to that achieved in the corresponding photochemical path. Thus, we show that the energy needed for switching spiropyrans to the merocyanine form on demand, typically delivered by a photon, can instead be provided electrochemically. This opens up further opportunities for the utilization of spiropyrans in electrically controlled applications and devices.

Excited State Structure Correlates with Efficient Photoconversion in Unidirectional Motors.

The design of unidirectional photomolecular motors demands a critical understanding of an ultrafast photochemical isomerization. An intermediate dark excited state mediates the reaction via a conical intersection (CI) with the ground state, but a correlation between molecular structure and photoisomerization efficiency has remained elusive. Here femtosecond stimulated Raman spectroscopy captures vibrational spectra of the dark state in a set of molecular motors bearing different substituents. A direct correlation between isomerization quantum yield, dark state lifetime, and excited state vibrational spectrum is found. Electron withdrawing substituents lead to activity in lower frequency modes, which we correlate with a pyramidalization distortion at the ethylenic axle occurring within 100 fs. This structure is not formed with an electron donating substituent, where the axle retains double bond character. Further structural reorganization is observed and assigned to excited state reorganization and charge redistribution on the sub-picosecond time scale. The correlation of the dark state structure with photoconversion performance suggests guidelines for developing new more efficient motor derivatives.

Photophysics of First-Generation Photomolecular Motors: Resolving Roles of Temperature, Friction, and Medium Polarity.

Light-driven unidirectional molecular rotary motors have the potential to power molecular machines. Consequently, optimizing their speed and efficiency is an important objective. Here, we investigate factors controlling the photochemical yield of the prototypical unidirectional rotary motor, a sterically overcrowded alkene, through detailed investigation of its excited-state dynamics. An isoviscosity analysis of the ultrafast fluorescence decay data resolves friction from barrier effects and reveals a 3.4 ± 0.5 kJ mol-1 barrier to excited-state decay in nonpolar media. Extension of this analysis to polar solvents shows that this barrier height is a strong function of medium polarity and that the decay pathway becomes near barrierless in more polar media. Thus, the properties of the medium can be used as a route for controlling the motor's excited-state dynamics. The connection between these dynamics and the quantum yield of photochemical isomerization is probed. The photochemical quantum yield is shown to be a much weaker function of solvent polarity, and the most efficient excited-state decay pathway does not lead to a strongly enhanced quantum yield for isomerization. These results are discussed in terms of the solvent dependence of the complex multidimensional excited-state reaction coordinate.

Observation of Ultrafast Coherence Transfer and Degenerate States with Polarization-Controlled Two-Dimensional Electronic Spectroscopy.

Optical spectroscopy is a powerful tool to interrogate quantum states of matter. We present simulation results for the cross-polarized two-dimensional electronic spectra of the light-harvesting system LH2 of purple bacteria. We identify a spectral feature on the diagonal, which we assign to ultrafast coherence transfer between degenerate states. The implication for the interpretation of previous experiments on different systems and the potential use of this feature are discussed. In particular, we foresee that this kind of feature will be useful for identifying mixed degenerate states and for identifying the origin of symmetry breaking disorder in systems like LH2. Furthermore, this may help identify both vibrational and electronic states in biological systems such as proteins and solid-state materials such as hybrid perovskites.

Visible-Light-Driven Rotation of Molecular Motors in a Dual-Function Metal-Organic Framework Enabled by Energy Transfer.

The visible-light-driven rotation of an overcrowded alkene-based molecular motor strut in a dual-function metal-organic framework (MOF) is reported. Two types of functional linkers, a palladium-porphyrin photosensitizer and a bispyridine-derived molecular motor, were used to construct the framework capable of harvesting low-energy green light to power the rotary motion. The molecular motor was introduced in the framework using the postsynthetic solvent-assisted linker exchange (SALE) method, and the structure of the material was confirmed by powder (PXRD) and single-crystal X-ray (SC-XRD) diffraction. The large decrease in the phosphorescence lifetime and intensity of the porphyrin in the MOFs upon introduction of the molecular motor pillars confirms efficient triplet-to-triplet energy transfer between the porphyrin linkers and the molecular motor. Near-infrared Raman spectroscopy revealed that the visible light-driven rotation of the molecular motor proceeds in the solid state at rates similar to those observed in solution.

Ultrafast Excited State Dynamics in a First Generation Photomolecular Motor.

Efficient photomolecular motors will be critical elements in the design and development of molecular machines. Optimisation of the quantum yield for photoisomerisation requires a detailed understanding of molecular dynamics in the excited electronic state. Here we probe the primary photophysical processes in the archetypal first generation photomolecular motor, with sub-50 fs time resolved fluorescence spectroscopy. A bimodal relaxation is observed with a 100 fs relaxation of the Franck-Condon state to populate a red-shifted state with a reduced transition moment, which then undergoes multi-exponential decay on a picosecond timescale. Oscillations due to the excitation of vibrational coherences in the S1 state are seen to survive the ultrafast structural relaxation. The picosecond relaxation reveals a strong solvent friction effect which is thus ascribed to torsion about the C-C axle. This behaviour is contrasted with second generation photomolecular motors; the principal differences are explained by the existence of a barrier on the excited state surface in the case of the first-generation motors which is absent in the second generation. These results will help to provide a basis for designing more efficient molecular motors in the future.