Correction: Photochromic spiropyran- and spirooxazine-homopolymers in mesoporous thin films by surface initiated ROMP

Krohm, Fabio; Kind, Jonas; Savka, Roman; Janssen, M.; Herold, Dominik; Plenio, Herbert; Thiele, Christina M.; Andrieu‐Brunsen, Annette

doi:10.1039/c6tc90045c

Cited by 2 publications

(3 citation statements)

References 1 publication

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“…1,37 The improved effective cross-section compared to spironaphthopyran or nitro-BIPS could originate from the formation of a singlet state instead of a triplet state upon UVexcitation as has been discussed for SOs in gels or films. 38,39 Our findings show that an efficient photochromism can also be achieved on the surface without a decoupling layer, which enhances the amount of possible applications and reduces the complexity of the system. This and the enhanced effective cross-section of the SNO-to-MC conversion constitute a huge leap forward in realization of photochromic molecular devices on solid surfaces.…”

Section: Resultsmentioning

confidence: 69%

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Highly Efficient and Bidirectional Photochromism of Spirooxazine on Au(111)

et al. 2018

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Controlling molecules in direct contact with surfaces is central to molecular electronics. Photochromic molecules immobilized and contacted by a surface promise to provide remote control on the molecular level using light. Combining x-ray absorption spectroscopy, differential reflectance spectroscopy, and density functional theory, we demonstrate highly efficient and bidirectional photochromism of a spirooxazine molecular switch in direct contact with a Au(111) surface. The ring-opening reaction by UV light is two orders of magnitude more efficient than previously reported for other surface-adsorbed systems and, even more importantly, the redlight-induced ring-closing is accessible even in contact with a metal surface. This opens new prospects for applications by utilizing the gold surface with directly adsorbed functional units consisting of molecular photochromic switches.

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Section: Resultsmentioning

confidence: 69%

“…This is a well-known photoconversion, intensely studied in various solutions, 36,37 gels, 38 or thin films. 39,40…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient and Bidirectional Photochromism of Spirooxazine on Au(111)

et al. 2018

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“…In order to couple UV-light into the reaction mixtures, a waveguide (BFH 48-1000, Thorlabs) was inserted within a coaxial stem insert (WGS-5BL-SP – Wilmad LabGlass) into the solution. ,,, For premonomer photolysis a Nichia SMD LED UV NCSU275 was used, driven at a current of 500 mA (Lumitronix). For photopolymerization UV-irradiation was applied by a Lumatec SUV 400 broad band light source in combination with a 320–400 nm filter (spectral intensity given in the Supporting Information).…”

Section: Methodsmentioning

confidence: 99%

Full Quantification of the Light-Mediated Gilch Polymerization

et al. 2018

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Alkoxy-substituted poly(p-phenylenevinylenes) (PPVs) continue to be major workhorse materials in optoelectronics, ranging from thin film electronics to bioimaging. An attractive synthetic route toward PPVs is the Gilch polymerization. Nevertheless, obtaining control over molecular weight and chain constitution is challenging due to the free-radical nature of this reaction. In this work we quantitatively show with in situ UV-irradiation NMR spectroscopy how control over the Gilch polymerization can be enhanced by irradiation with UV-light. The potential of this method has been demonstrated but never interpreted within a quantitative framework, resulting in a lack of mechanistic and kinetic insight. We account for this not only by in situ analyzing and modeling the photochemical Gilch polymerization but also by characterizing the photolysis of the starting material. The latter shows that the solvent THF likely acts as radical transfer agent in the Gilch pathway and similar precursor-based biradical routes. We perform two photopolymerization runs: (i) under continuous UV-irradiation and (ii) by applying a short UV pulse while monitoring the chemical response of the mixture. Since existing models of the Gilch polymerization are inadequate for describing the recorded time−concentration profiles, we develop a new model that couples thermal and photoinduced polymerization. Numerical curve fitting quantifies the rate constants associated with both pathways. We demonstrate that (i) a photoactivated p-quinodimethane species Q* reacts in the (re)initiation and propagation steps, (ii) photopropagation is significantly faster than photoinitiation, and (iii) the photochemical reactions are considerably faster than their thermal analogues, which allows for decoupling the thermal and photochemical pathways at temperatures low enough to suppress the former.

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Correction: Photochromic spiropyran- and spirooxazine-homopolymers in mesoporous thin films by surface initiated ROMP

Cited by 2 publications

References 1 publication

Highly Efficient and Bidirectional Photochromism of Spirooxazine on Au(111)

Highly Efficient and Bidirectional Photochromism of Spirooxazine on Au(111)

Full Quantification of the Light-Mediated Gilch Polymerization

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