5 research outputs found

    Effect of Immobilization on Gold on the Temperature Dependence of Photochromic Switching of Dithienylethenes

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    We report the properties and switching characteristics of a series of dithienylethene photochromic switches immobilized on gold. Self-assembled monolayers (SAMs) of three structurally related dithienylethenes were formed on roughened gold bead substrates and studied by surface-enhanced Raman spectroscopy (SERS). These data were compared to SERS spectra obtained by aggregation of colloidal gold, solid state Raman spectra, and Raman spectra calculated using density functional theory (DFT). Two of the dithienylethenes studied have an “asymmetric” design, which was demonstrated earlier to lower the thermal barrier for photochemical ring opening in solution. Herein, we show that, when immobilized on a gold surface, the asymmetric dithienylethenes in fact display a higher thermal barrier than that of their symmetric counterparts. In addition, we show that photochemical ring closing of asymmetric dithienylethenes is inhibited when immobilized on gold

    Tuning the Temperature Dependence for Switching in Dithienylethene Photochromic Switches

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    Diarylethene photochromic switches use light to drive structural changes through reversible electrocyclization reactions. High efficiency in dynamic photoswitching is a prerequisite for applications, as is thermal stability and the selective addressability of both isomers ring-opened and -closed diarylethenes. These properties can be optimized readily through rational variation in molecular structure. The efficiency with regard to switching as a function of structural variation is much less understood, with the exception of geometric requirements placed on the reacting atoms. Ultimately, increasing the quantum efficiency of photochemical switching in diarylethenes requires a detailed understanding of the excited-state potential energy surface(s) and the mechanisms involved in switching. Through studies of the temperature dependence, photoswitching and theoretical studies demonstrate the occurrence or absence of thermal activation barriers in three constitutional isomers that bear distinct π-conjugated systems. We found that a decrease in the thermal barriers correlates with an increase in switching efficiency. The origin of the barriers is assigned to the decrease in π-conjugation that is concomitant with the progress of the photoreaction. Furthermore, we show that balanced molecular design can minimize the change in the extent of π-conjugation during switching and lead to optimal bidirectional switching efficiencies. Our findings hold implications for future structural design of diarylethene photochromic switches

    Electron-Transfer Rates in Host–Guest Assemblies at β‑Cyclodextrin Monolayers

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    The effect of the distance between a β-cyclodextrin (βCD) host core and a conductive substrate on the electron-transfer rate of complexed guests as well as of free-diffusing electrochemically active probes has been studied. First we have evaluated a set of short-tethered βCD adsorbates bearing different anchoring groups in order to get a reliable platform for the study of short-distance electron transfer. An electrochemically active trivalent guest was immobilized on these host monolayers in a selective and reversible manner, providing information about the packing density. Iodine- and nitrile-functionalized βCD monolayers gave coverages close to maximum packing. Electron transfer in the presence of Fe­(CN)<sub>6</sub><sup>3–/4–</sup> studied by impedance spectroscopy revealed that the electron transfer of the diffusing probe was 3 orders of magnitude faster than when the βCD cores were separated from the surface by undecyl chains. When an electrochemically active guest was immobilized on the surface, electron-transfer rate measurements by cyclic voltammetry and capacitance spectroscopy showed differences of up to a factor of 8 for different βCD monolayers. These results suggest that increasing the distance between the βCD core and the underlying conductive substrate leads to a diminishing of the electron-transfer rate

    Monolayer Contact Doping from a Silicon Oxide Source Substrate

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    Monolayer contact doping (MLCD) is a modification of the monolayer doping (MLD) technique that involves monolayer formation of a dopant-containing adsorbate on a source substrate. This source substrate is subsequently brought into contact with the target substrate, upon which the dopant is driven into the target substrate by thermal annealing. Here, we report a modified MLCD process, in which we replace the commonly used Si source substrate by a thermally oxidized substrate with a 100 nm thick silicon oxide layer, functionalized with a monolayer of a dopant-containing silane. The thermal oxide potentially provides a better capping effect and effectively prevents the dopants from diffusing back into the source substrate. The use of easily accessible and processable silane monolayers provides access to a general and modifiable process for the introduction of dopants on the source substrate. As a proof of concept, a boron-rich carboranyl-alkoxysilane was used here to construct the monolayer that delivers the dopant, to boost the doping level in the target substrate. X-ray photoelectron spectroscopy (XPS) showed a successful grafting of the dopant adsorbate onto the SiO<sub>2</sub> surface. The achieved doping levels after thermal annealing were similar to the doping levels acessible by MLD as demonstrated by secondary ion mass spectrometry measurements. The method shows good prospects, e.g. for use in the doping of Si nanostructures

    Synthesis and Controlled Self-Assembly of Covalently Linked Hexa-<i>peri</i>-hexabenzocoronene/Perylene Diimide Dyads as Models To Study Fundamental Energy and Electron Transfer Processes

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    We report the synthesis and photophysical characterization of a series of hexa-<i>peri</i>-hexabenzocoronene (HBC)/perylenetetracarboxy diimide (PDI) dyads that are covalently linked with a rigid bridge. Both the ratio of the two components and the conjugation of the bridging element are systematically modified to study the influence on self-assembly and energy and electron transfer between electron donor HBC and acceptor PDI. STM and 2D-WAXS experiments reveal that both in solution and in bulk solid state the dyads assemble into well-ordered two-dimensional supramolecular structures with controllable mutual orientations and distances between donor and acceptor at a nanoscopic scale. Depending on the symmetry of the dyads, either columns with nanosegregated stacks of HBC and PDI or interdigitating networks with alternating HBC and PDI moieties are observed. UV–vis, photoluminescence, transient photoluminescence, and transient absorption spectroscopy confirm that after photoexcitation of the donor HBC a photoinduced electron transfer between HBC and PDI can only compete with the dominant Förster resonance energy transfer, if facilitated by an intimate stacking of HBC and PDI with sufficient orbital overlap. However, while the alternating stacks allow efficient electron transfer, only the nanosegregated stacks provide charge transport channels in bulk state that are a prerequisite for application as active components in thin film electronic devices. These results have important implications for the further design of functional donor–acceptor dyads, being promising materials for organic bulk heterojunction solar cells and field-effect transistors