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    Tenfold increase in the photostability of an azobenzene guest in vapor-deposited glass mixtures

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    Figure 1. Photoisomerization of glasses containing 5% DPA guest in a matrix of celecoxib as monitored by absorbance after light irradiation at 365 nm; irradiation times are specified in the legend..opj (254.5Kb)
    Figure 2. Time dependence of photoisomerization for vapor-deposited and liquid-cooled (LC) glasses of 5% DPA in celecoxib as determined from normalized absorbance at 370 nm..opj (305.1Kb)
    Figure 3. Photostability of vapor-deposited glasses, with comparison to the liquid-cooled (LC) glass and DPA in solution..opj (94.95Kb)
    Figure 4. Density changes during illumination for vapor-deposited and liquid-cooled glasses of celecoxib with 5% DPA, as a function of irradiation time..opj (121.3Kb)
    Figure 5. Thickness changes obtained by ellipsometry for a vapor-deposited glass of celecoxib during temperature cycling.opj (8.335Mb)
    Figure 6. Summary of (a) relative density, (b) onset temperature, and (c) birefringence (nz – nxy) of vapor-deposited neat films of celecoxib (blue points) and mixtures with 5% DPA (red points).opj (220.1Kb)
    Figure 7. Correlation of photoisomerization rate constant with the density of vapor-deposited glasses of the celecoxib host..opj (84.50Kb)
    Figure 8. Photoisomerization from trans to cis states as observed in molecular simulations for a mixed glass (5% isomerizable guests), for glasses vapor-deposited at different substrate temperatures..opj (947.0Kb)
    Figure 9. Simulation results showing photo-induced density changes for glasses with different fractions of isomerizable guests..opj (160.2Kb)
    Figure 10. Density change in simulations after 800 photoexcitation events for glasses with different guest fractions..opj (39.32Kb)
    Figure S1. Glass density as a function of normalized substrate temperature for vapor-deposited and liquid-cooled (LC) glasses in computer simulations..opj (38.23Kb)
    Scheme 1.Photoisomerization of 4,4’-diphenylazobenzene (DPA) under UV irradiation..wmf (47.02Kb)
    Date
    2018-09-10
    Author
    Ediger, Mark
    de Pablo, Juan
    Torkelson, John
    Antony, Lucas
    Qiu, Yue
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    Abstract
    Improvements to the photostability of organic glasses for use in electronic applications have generally relied on modification of chemical structure. We show here that the photostability of a guest molecule can also be significantly improved - without chemical modification - by using physical vapor deposition to pack molecules more densely. Photoisomerization of the substituted azobenzene, 4,4’-diphenyl azobenzene (DPA), was studied in a vapor-deposited glass matrix of celecoxib. We directly measure photoisomerization of trans- to cis- states via UV-Vis spectroscopy and show that the rate of photoisomerization depends upon the substrate temperature used during co-deposition of the glass. Photostability correlates with the density of the glass, where the optimum glass is about tenfold more photostable than the liquid-cooled glass. Molecular simulations, which mimic photoisomerization, also demonstrate that photoreaction of a guest molecule can be suppressed in vapor-deposited glasses. From the simulations, we estimate that the region that is disrupted by a single photoisomerization event encompasses approximately 5 molecules.
    Subject
    photostablity, azobenzene, vapor deposition, organic glasses, mixture
    Permanent Link
    http://digital.library.wisc.edu/1793/78702
    Related Material/Data
    10.1063/1.5052003
    Type
    Dataset
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    • Ediger Research Group

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