ABSTRACT
Among inherently chiral selectors of axial stereogenicity, usually resulting in very good enantiodiscrimination performances, the biindole-based family has the additional advantage of very easy functionalization of the two nitrogen atoms with a variety of substituents with desirable properties. Aiming to evaluate the possibility of exploiting such feature to enhance the enantiodiscrimination ability of the archetype structure, a series of three inherently chiral monomers were designed and synthesized, characterised by a 2,2'-biindole atropisomeric core conjugated to bithiophene wings enabling fast and regular electrooligomerization, and functionalised at the nitrogen atoms with an ethyl, a methoxyethyl, or a hydroxyethyl substituent. Nitrogen alkylation was also exploited to obtain for the first time the chemical resolution of the biindole selectors without employing chiral HPLC. The enantiodiscrimination ability of the selector series was comparatively evaluated in proof-of-concept chiral voltammetry experiments with a "benchmark" chiral ferrocenyl probe as well as with chiral non-steroidal anti-inflammatory drugs naproxen and ketoprofen. The large enantiomer potential differences for all probes increased in the ethyl < methoxyethyl ⪠hydroxyethyl sequence of selector substituents, supporting our assumption on the beneficial role of an additional coordination element. The powerful hydroxyethyl selector was also applied to ketoprofen in a commercial drug matrix.
ABSTRACT
The extent to which electrophores covalently bridged by a saturated linker are electrochemically independent was investigated considering the charge/spin duality of the electron and functionality of the electrophore as a spin carrier upon reduction. By combining computational modeling with electrochemical experiments, we investigated the mechanism by which tethered electrophores react together within 4,4'-oligo[n]methylene-bipyridinium assemblies (with n=2 to 5). We show that native dicationic electrophores (redox state Z=+2) are folded prior to electron injection into the system, allowing the emergence of supra-molecular orbitals (supra-MOs) likely to support the process of the reductive σ bond formation giving cyclomers. Indeed, for Z=+2, London Dispersion (LD) forces contribute to flatten the potential energy surface such that all-trans and folded conformers are approximately isoenergetic. Then, upon one-electron injection, for radical cations (Z=+1), LD forces significantly stabilize the folded conformers, except for the ethylene derivative deprived of supra-MOs. For radical cations equipped with supra-MOs, the unpaired electron is delocalized over both heterocycles through space. Cyclomer completion (Z=0) upon the second electron transfer occurs according to the inversion of redox potentials. This mechanism explains why intramolecular reactivity is favored and why pyridinium electrophores are not independent.
ABSTRACT
Self-assembled monolayers (SAMs) of terpyridine-based transition metal (ruthenium and osmium) complexes, anchored to gold substrate via tripodal anchoring groups, have been investigated as possible redox switching elements for molecular electronics. An electrochemical study was complemented by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) methods. STM was used for determination of the SAM conductance values, and computation of the attenuation factor ß from tunneling current-distance curves. We have shown that SAMs of Os-tripod molecules contain larger adlayer structures compared with SAMs of Ru-tripod molecules, which are characterized by a large number of almost evenly distributed small islands. Furthermore, upon cyclic voltammetric experimentation, Os-tripod films rearrange to form a smaller number of even larger islands, reminiscent of the Ostwald ripening process. Os-tripod SAMs displayed a higher surface concentration of molecules and lower conductance compared with Ru-tripod SAMs. The attenuation factor of Os-tripod films changed dramatically, upon electrochemical cycling, to a higher value. These observations are in accordance with previously reported electron transfer kinetics studies.
Subject(s)
Gold , Microscopy, Scanning Tunneling , Microscopy, Atomic Force , Surface Properties , Gold/chemistry , Oxidation-ReductionABSTRACT
The synergistic functioning of redox-active components that emerges from prototypical 2,2'-di(N-methylpyrid-4-ylium)-1,1'-biphenyl is described. Interestingly, even if a trans conformation of the native assembly is expected, due to electrostatic repulsion between cationic pyridinium units, we demonstrate that cis conformation is equally energy-stabilized on account of a peculiar LUMO (SupLUMO) that develops through space, encompassing the two pyridiniums in a single, made-in-one-piece, electronic entity (superelectrophoric behavior). This SupLUMO emergence, with the cis species as superelectrophore embodiment, originates in a sudden change of electronic structure. This finding is substantiated by insights from solid state (single-crystal X-ray diffraction) and solution (NOE NMR and UV-vis-NIR spectroelectrochemistry) studies, combined with electronic structure computations. Electrochemistry shows that electron transfers are so strongly correlated that two-electron reduction manifests itself as a single-step process with a large potential inversion consistent with inner creation of a carbon-carbon bond (digital simulation). Besides, absence of reductive formation of dimers is a further indication of a preferential intramolecular reactivity determined by the SupLUMO interaction (cis isomer pre-organization). The redox-gated covalent bond, serving as electron reservoir, was studied via atropisomerism of the reduction product (VTâ NMR study). The overall picture derived from this in-depth study of 2,2'-di(N-methylpyrid-4-ylium)-1,1'-biphenyl proves that trans and cis species are worth considered as intrinsically sharply different, that is, as doubly-electrophoric and singly-superelectrophoric switchable assemblies, beyond conformational isomerism. Most importantly, the through-space-mediated SupLUMO may come in complement of other weak interactions encountered in Supramolecular Chemistry as a tool for the design of electroactive architectures.
Subject(s)
Electronics , Crystallography, X-Ray , Electrochemistry , Magnetic Resonance Spectroscopy , Molecular ConformationABSTRACT
Environmental control of single-molecule junction evolution and conductance was demonstrated for expanded pyridinium molecules by scanning tunneling microscopy break junction method and interpreted by quantum transport calculations including solvent molecules explicitly. Fully extended and highly conducting molecular junctions prevail in water environment as opposed to short and less conducting junctions formed in non-solvating mesitylene. A theoretical approach correctly models single-molecule conductance values considering the experimental junction length. Most pronounced difference in the molecular junction formation and conductance was identified for a molecule with the highest stabilization energy on the gold substrate confirming the importance of molecule-electrode interactions. Presented concept of tuning conductance through molecule-electrode interactions in the solvent-driven junctions can be used in the development of new molecular electronic devices.
ABSTRACT
Molecular-level multielectron handling toward electrical storage is a worthwhile approach to solar energy harvesting. Here, a strategy which uses chemical bonds as electron reservoirs is introduced to demonstrate the new concept of "structronics" (a neologism derived from "structure" and "electronics"). Through this concept, we establish, synthesize, and thoroughly study two multicomponent "super-electrophores": 1,8-dipyridyliumnaphthalene, 2, and its N,N-bridged cyclophane-like analogue, 3. Within both of them, a covalent bond can be formed and subsequently broken electrochemically. These superelectrophores are based on two electrophoric (pyridinium) units that are, on purpose, spatially arranged by a naphthalene scaffold. A key characteristic of 2 and 3 is that they possess a LUMO that develops through space as the result of the interaction between the closely positioned electrophoric units. In the context of electron storage, this "super-LUMO" serves as an empty reservoir, which can be filled by a two-electron reduction, giving rise to an elongated C-C bond or "super-HOMO". Because of its weakened nature, this bond can undergo an electrochemically driven cleavage at a significantly more anodic-yet accessible-potential, thereby restoring the availability of the electron pair (reservoir emptying). In the representative case study of 2, an inversion of potential in both of the two-electron processes of bond formation and bond-cleavage is demonstrated. Overall, the structronic function is characterized by an electrochemical hysteresis and a chemical reversibility. This structronic superelectrophore can be viewed as the three-dimensional counterpart of benchmark methyl viologen (MV).
ABSTRACT
Adsorption properties of a series of redox-active expanded pyridinium molecules were studied at an electrified interface by cyclic and alternating current voltammetry methods. It was shown that the adsorbed state can sufficiently block N-pyramidalization of the pyridinium redox center of 2',6'-diphenyl-[4,1':4',4''-terpyridin]-1'-ium tetrafluoroborate (2), leading to a change of the mechanism from a single two-electron-transfer process to stepwise transfer of two electrons. Chemically locked molecules 1, 9-(pyridin-4-yl)benzo[ c]benzo[1,2]quinolizino[3,4,5,6- ija][1,6]naphthyridin-15-ium tetrafluoroborate (ring fusion), and 3, 3,5-dimethyl-2',6'-diphenyl-[4,1':4',4''-terpyridin]-1'-ium tetrafluoroborate (steric hindrance) do not enable N-pyramidalization of the redox center upon electron transfer (ET) and serve as references. It was shown that 1 follows Langmuir-type adsorption around a potential of zero charge and that 1-3 form a close-packed film with some repulsive interactions between individual molecules at potentials where ET takes place. It has been suggested that all three molecules lie flat on the electrode surface, with the lowest free energy of adsorption found for 2. Maximum surface concentration Γ* equal to (1.4 ± 0.1) × 10-10 mol·cm-2 was found for 1, (1.5 ± 0.1) × 10-10 mol·cm-2 for 2, and (1.6 ± 0.1) × 10-10 mol·cm-2 for 3. These findings will help to clarify the role of molecular contacts with conducting substrate in the single-molecule electron-transport measurements of 1-3 during the metal-molecule-metal junction formation process.
ABSTRACT
The efficient synthesis of tripodal platforms based on tetraphenylmethane with three acetyl-protected thiol groups in either meta or para positions relative to the central sp(3) carbon for deposition on Au (111) surfaces is reported. These platforms are intended to provide a vertical arrangement of the substituent in positionâ 4 of the perpendicular phenyl ring and an electronic coupling to the gold substrate. The self-assembly features of both derivatives are analyzed on Au (111) surfaces by low-temperature ultra-high-vacuum STM, high-resolution X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and reductive voltammetric desorption studies. These experiments indicated that the meta derivative forms a well-ordered monolayer, with most of the anchoring groups bound to the surface, whereas the para derivative forms a multilayer film with physically adsorbed adlayers on the chemisorbed para monolayer. Single-molecule conductance values for both tripodal platforms are obtained through an STM break junction experiment.
ABSTRACT
A combined electrochemical and theoretical study of a series of pyridinium-based electrophores, consisting of reference N-alkyl-2,4,6-triarylpyridiniums (1-3) and N-aryl-expanded pyridiniums (EPs), i.e. N-aryl-2,4,6-triarylpyridiniums (4-10), is presented with the aim of elucidating multifaceted mechanisms underpinning the complex electrophoric activity of fluxional EP systems. Series 1-10 constitutes a library of model electrophores showing an incremental variation of their composition, charge, and steric hindrance. By kinetic mapping of the first two heterogeneous electron transfers (ETs) of 1-10 and computational mapping, at the density functional theory level, of their electronic and geometrical features in various redox states, it is established that, depending on whether EPs are made of one (4, 5) or two "head-to-tail"-connected pyridinium rings (6-10), the nature of the redox-triggered distortions (when allowed) is different, namely, N-pyramidalization due to hybridization change in the former case versus saddle-shaped distortion originating from conflicting intramolecular interactions in the latter case (8-10). When skeletal relaxations are sterically hampered, zwitterionic states and electron delocalization with quinoidal features are promoted as alternative relaxation modes. It follows that "potential compression" is changed to "potential expansion" (i.e., a further separation of redox potentials) in single-pyridinium EPs (4, 5), whereas "potential inversion" (i.e., single-step two-electron transfer; 8-10) is changed to stepwise ETs of the Weitz type for two-pyridinium EPs (6, 7). Overall, kinetic rate constants not only consistently indicate the most prominent mechanistic aspects of the reduction pathways of EPs, but they are also instrumental in establishing EPs as a unique class of electrophores.
ABSTRACT
Two-step redox switching in enantiopure helquat system [P-1](2+) â [P-1](â¢+) â [P-1](0) is demonstrated. The viologen-type electroactive unit embedded directly in the helical scaffold of 1 is responsible for the prominent chiroptical switching at 264 nm. This process is associated with a marked sign-reversal of Cotton effect ramping between Δε = +35 M(-1) cm(-1) for [P-1](2+) and Δε = -100 M(-1) cm(-1) for [P-1](0). This helically chiral system features the most intense chiroptical switch response documented in the field of helicenoids.
ABSTRACT
BACKGROUND: Spectroelectrochemistry (SEC) is a valuable analytical tool providing insights to reaction mechanisms and the structure of species involved in charge transfer reactions. Most of commercial SEC setups are based on platinum working electrodes where the adsorption of species involved in reactions often complicates their analysis. RESULTS: In this work, we employ an array of pencil graphite rods as an optically transparent working electrode in a custom-made air-tight thin-layer cell suitable for the SEC analysis performed here in acetonitrile as a representative non-aqueous solvent. The functionality of the device was demonstrated by UV-Vis SEC sensing of charge transfer reactions of ruthenium acetylacetonate, ferrocene and ethylviologen dibromide redox probes performed employing the cyclic voltammetry. The SEC response obtained for all three probes confirmed no adsorption and the absence of oxygen in the cell. Furthermore, we have developed and utilized finite element method numerical simulations considering charge transfer reactions coupled with the diffusional mass transport to model the cyclic voltammetric response and the reaction conversion in the thin-layer SEC cell. SIGNIFICANCE: Our work paves the way for easy-to-assemble customized air-tight adsorption-free SEC devices with the manufacturing costs well below those of commercially available platforms. Developed computational approaches have the predictive power for optimizing reaction conditions and the geometry of the SEC cell.
ABSTRACT
Short monodisperse oligo- (para-phenyleneethynylene) (pOPE) units bearing laterally attached tetrathio-substituted tetrathiofulvalene (TTF) units have been synthesised from functionalised aromatic building blocks by using the Sonogashira cross-coupling methodology. The unusual redox properties of these TTF-pOPE conjugates were observed by employing electrochemical methods, such as cyclic voltammetry and exhaustive electrolysis. We found that formally one half of the TTF units in the pOPE monomer 1, dimer 2, and trimer 3 (with 2, 4, and 6 TTF units, respectively) are electrochemically silent during the first-step oxidation at 0.49â V. We propose the formation of persistent mixed-valence complexes from the TTF and TTF(+·) units present in an equal ratio. Such mixed-valence dyads (single or multiple in the partially oxidised 1-3) exhibit an unusual stability towards oxidation until the potential of the second oxidation at 0.84â V is achieved. This finding suggests that below this potential the oxidation of the respective mix-valence complexes is extremely slow.
ABSTRACT
As a part of our objective to build an immunosensor for the detection of the pesticide atrazine (ATZ) in environmental samples, we studied the self-assembling process of the disulfide derivative of the pesticide atrazine on a gold substrate. Atrazine-based self-assembled monolayers were characterized by ellipsometry, scanning tunneling microscopy, polarization-modulation infrared reflection-absorption spectroscopy (PM IRRAS), X-ray photoelectron spectroscopy and quartz crystal microbalance (QCM) measurements. Two different time constants for the adsorption process were observed, depending on the experimental method used. The QCM data reflect adsorption kinetics of the original disulfide compound, whereas ellipsometry and ex situ PM IRRAS refer to the formation of thiolate (ATZS) monolayers. In situ QCM data demonstrated the suitability of such monolayers for the detection of atrazine in aqueous samples. Exposure of the ATZS sensing surface to an anti-atrazine antibody (anti-ATZ IgG) resulted in complete coverage of the surface by antibody, whereas approximately half of the antibody molecules were displaced from the QCM sensor surface by further addition of atrazine into the solution.
Subject(s)
Antibodies, Immobilized , Antibodies/chemistry , Atrazine/chemistry , Biosensing Techniques , Gold/chemistry , Immunoassay/instrumentation , Microscopy, Electron, Scanning , Molecular Structure , Spectroscopy, Fourier Transform Infrared , Surface PropertiesABSTRACT
The synthesis, characterization, redox behavior, and photophysical properties (both at room temperature in fluid solution and at 77 K in rigid matrix) of a series of four new molecular dyads (2-5) containing Ru(II)- or Os(II)-bis(terpyridine) subunits as chromophores and various expanded pyridinium subunits as electron acceptors are reported, along with the reference properties of a formerly reported dyad, 1. The molecular dyads 2-4 have been designed to have their (potentially emissive) triplet metal-to-ligand charge-transfer (MLCT) and charge-separated (CS) states close in energy, so that excited-state equilibration between these levels can take place. Such a situation is not shared by limit cases 1 and 5. For dyad 1, forward photoinduced electron transfer (time constant, 7 ps) and subsequent charge recombination (time constant, 45 ps) are evidenced, while for dyad 5, photoinduced electron transfer is thermodynamically forbidden so that MLCT decays are the only active deactivation processes. As regards 2-4, CS states are formed from MLCT states with time constants of a few dozens of picoseconds. However, for these latter species, such experimental time constants are not due to photoinduced charge separation but are related to the excited-state equilibration times. Comparative analysis of time constants for charge recombination from the CS states based on proper thermodynamic and kinetic models highlighted that, in spite of their apparently affiliated structures, dyads 1-4 do not constitute a homologous series of compounds as far as intercomponent electron transfer processes are concerned.
ABSTRACT
Recent advances in fused deposition modelling 3D printing (FDM 3DP) and synthesis of printable electrically conductive materials enabled the manufacture of customized electrodes and electrochemical devices by this technique. The past couple of years have seen a boom in applying approaches of FDM 3DP in the realm of spectroelectrochemistry (SEC). Despite significant progress, reported designs of SEC devices still rely on conventionally manufactured optical components such as quartz windows and cuvettes. To bridge this technological gap, in this work we apply bi-material FDM 3DP combining electrically conductive and optically translucent filaments to manufacture working electrodes and cells, constituting a fully integrated microfluidic platform for transmission absorption UV-Vis SEC measurements. The cell design enables de-aeration of samples and their convenient handling and analysis. Employing cyclic voltammetric measurements with ruthenium(III) acetylacetonate, ethylviologen dibromide and ferrocenemethanol redox-active probes as model analytes, we demonstrate that the presented platform allows SEC sensing of reactants, intermediates and products of charge transfer reactions, including the inspection of their long-term stability. Approaches developed and presented in this work pave the way for manufacturing customized SEC devices with dramatically reduced costs compared to currently available commercial platforms.
ABSTRACT
Contrary to 4,4'-dipyridinium (i.e., archetypal methyl viologen), which is reduced by two single-electron transfers (stepwise reduction), the 4,1'-dipyridinium isomer (so-called "head-to-tail" isomer) undergoes two electron transfers at apparently the same potential (single-step reduction). A combined theoretical and experimental study has been undertaken to establish that the latter electrochemical behavior, also observed for other polyarylpyridinium electrophores, is due to potential compression originating in a large structural rearrangement. Three series of branched expanded pyridiniums (EPs) were prepared: N-aryl-2,4,6-triphenylpyridiniums (Ar-TP), N-aryl-2,3,4,5,6-pentaphenylpyridiniums (Ar-XP), and N-aryl-3,5-dimethyl-2,4,6-triphenylpyridinium (Ar-DMTP). The intramolecular steric strain was tuned via N-pyridinio aryl group (Ar) phenyl (Ph), 4-pyridyl (Py), and 4-pyridylium (qPy) and their bulky 3,5-dimethyl counterparts, xylyl (Xy), lutidyl (Lu), and lutidylium (qLu), respectively. Ferrocenyl subunits as internal redox references were covalently appended to representative electrophores in order to count the electrons involved in EP-centered reduction processes. Depending on the steric constraint around the N-pyridinio site, the two-electron reduction is single-step (Ar = Ph, Py, qPy) or stepwise (Ar = Xy, Lu, qLu). This steric switching of the potential compression is accurately accounted for by ab initio modeling (Density Functional Theory, DFT) that proposes a mechanism for pyramidalization of the N(pyridinio) atom coupled with reduction. When the hybridization change of this atom is hindered (Ar = Xy, Lu, qLu), the first reduction is a one-electron process. Theory also reveals that the single-step two-electron reduction involves couples of redox isomers (electromers) displaying both the axial geometry of native EPs and the pyramidalized geometry of doubly reduced EPs. This picture is confirmed by a combined UV-vis-NIR spectroelectrochemical and time-dependent DFT study: comparison of in situ spectroelectrochemical data with the calculated electronic transitions makes it possible to both evidence the distortion and identify the predicted electromers, which play decisive roles in the electron-transfer mechanism. Last, this mechanism is further supported by in-depth analysis of the electronic structures of electrophores in their various reduction states (including electromeric forms).
Subject(s)
Electrons , Polymers/chemistry , Pyridinium Compounds/chemistry , Molecular Structure , Oxidation-ReductionABSTRACT
Facile electron transfer in molecules with one dimension greatly exceeding the other two is essential in the development of new molecular electronic devices as these molecules can serve as so-called molecular wires. In this communication the electrochemical behavior of a series of molecules with multiple extended viologen moieties has been studied. We show that the electron transfer in the shortest wire is due to reduction of two identical communicating pyridinium moieties leading to a full charge delocalization, whereas the electron transfer in molecules with n≥ 2 is due to reduction of initially non-communicating centers. This was confirmed by digital simulation of cyclic voltammograms. All studied molecules accept reversibly at least four and up to ten electrons without any long-term chemical changes, which is a prerequisite for their future application. Chemical stability of these molecules after multiple electron transfer was confirmed by in situ UV-Vis spectroelectrochemical detection.
ABSTRACT
A long organic molecule 1 with five bipyridinium functions separated by benzene rings (extended viologen) undergoes a reversible multi-step electron transfer. Here we show that this decacation accepts electrons at the heterogeneous interface with the occurrence of the periodically changing electric reduction currents. According to the applied bias voltage the observed current-time dependence changes from chaotic through periodic and irregular to sinusoidal and finally to monotonous. A careful choice of the controlling parameters yields the sustained periodic sinusoidal currents lasting for a prolonged time. Oscillations stem from a mutual interplay of the heterogeneous supply of electrons and the homogeneous redox reactions (disproportionation) between the transient redox forms. In difference to many other electrochemical oscillating systems the described oscillations do not require any additional external impedance. The principle of these oscillatory currents may serve as a model of a truly 'molecular oscillator'.
ABSTRACT
Extended viologens represent a group of organic molecules intended to be used as molecular wires in molecular electronic devices. Adsorption properties of a novel series of extended viologen molecules were studied at the mercury electrode|electrolyte interface. These compounds form compact monolayers around the potential of zero charge with a constant differential capacitance value of 2.5 ± 0.2 µF cm(-2) independent of temperature, length of the molecule, and its bulk concentration. At more negative potentials their reduction in the adsorbed state takes place. We showed that the adsorption process is diffusion controlled and time needed to fully cover the electrode surface is independent of the electrode potential. A modified Koryta equation was employed for the calculation of the surface concentration of the adsorbates leading to the value of 5.3 × 10(-11) mol cm(-2) for the shortest wire and to 1.6 × 10(-11) mol cm(-2) for the longest one. Based on the space filling model and the differential capacitance value in the compact film region, it was postulated that these molecules lay flat on the electrode surface.
ABSTRACT
A transfer of fullerene C(60) to water was achieved by sonication of a two-phase system of water and C(60) in organic solvents, namely, benzene and toluene. Resulting aqueous dispersions were analyzed electrochemically, spectroscopically, by MALDI-MS and AFM methods. Samples prepared from benzene yield the formal redox potential very close to a value expected from the correlation of redox potentials and solvent donor numbers. However, these samples are not stable and C(60) precipitates out of the aqueous dispersion. Sonication of the toluene/water system produces stable system, in which the measured formal redox potential of C(60) is less negative. Stabilization of C(60) clusters in water is achieved by the presence of an organic amphiphile and spectroscopic methods indicate the presence of benzoate formed during sonication of a toluene/water mixture.