Sensitive Assays by Nucleophile-Induced Rearrangement of Photoactivated Diarylethenes

Fredrich, Sebastian; Bonasera, Aurelio; Valderrey, Virginia; Hecht, Stefan

doi:10.1021/jacs.8b02982

Cited by 46 publications

(42 citation statements)

References 59 publications

(91 reference statements)

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“…Synthesis of o ‐ATE was accomplished by an initial Pd‐catalyzed cross‐coupling between cyclohexanone and 3‐bromo‐2‐methyl‐5‐[4‐(trifluoromethyl)phenyl]thiophene followed by conversion into the corresponding enol triflate. Subsequently, the guaiazulenyl moiety was introduced via Suzuki coupling involving 2‐guaiazulenylboronic acid pinacol ester (see Scheme S1).…”

Section: Figurementioning

confidence: 99%

Proton‐Gated Ring‐Closure of a Negative Photochromic Azulene‐Based Diarylethene

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Proton-responsive photochromic molecules are attractive for their ability to react on non-invasive rapid optical stimuli and the importance of protonation/deprotonation processes in various fields. Conventionally, their acidic/basic sites are on hetero-atoms, which are orthogonal to the photoactive p-center. Here, we incorporate azulene, an acid-sensitive pure hydrocarbon, into the skeleton of a diarylethene-type photoswitch. The latter exhibits a novel proton-gated negative photochromic ring-closure and its optical response upon protonation in both open and closed forms is much more pronounced than those of diarylethene photoswitches with hetero-atom based acidic/basic moieties. The unique behavior of the new photoswitch can be attributed to direct protonation on its p-system, supported by 1 H NMR and theoretical calculations. Our results demonstrate the great potential of integrating non-alternant hydrocarbons into photochromic systems for the development of multi-responsive molecular switches.

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Section: Figurementioning

confidence: 99%

Proton‐Gated Ring‐Closure of a Negative Photochromic Azulene‐Based Diarylethene

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“…Thus, simplified motifs for switches or motors should be investigated as potentially more practical analogues of current complex synthetic molecules. But also “low‐tech” applications in the context of enabling the developing world, for example, cheap diagnostics, should be explored . With this in mind, we should critically remind the field that at this point in time, the only massively commercially successful application of photoswitchable materials has been photochromic lenses for adaptive sunglasses.…”

Section: Discussionmentioning

confidence: 99%

Enlightening Materials with Photoswitches

2020

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reversible conversion between their stable and (meta)stable isomers triggered by light. The return to their native, thermo dynamically most stable isomer is gener ally induced by using another wavelength of light or simply by heat, depending on the thermal stability of the (meta)stable isomer. Retinal-the prototypical photo switch in biology-showcases impressively how structural changes occurring during a lightinduced doublebond isomerization can lead to vision or allow microorganisms to convert photons into metabolic energy. In analogy, over the years, scientists have learned that the lightdriven isomeriza tion of small molecules can be collected, possibly amplified, and transformed into macroscopic property changes, such as mechanical motion, [1] charge carrying ability, [2] assembly and disassembly of macroscopic aggregates, [3] as well as switching of surfaces and their properties. [4] Materials, which for the purpose of this review are consid ered to be solid objects or organized assemblies in solution, provide unique advantages to enhance the function of photo switches and even create new functions when compared to their standalone molecular selves (for the primarily discussed photochromic molecules herein, see Figure 1). One must, how ever, consider the inherent challenges that may present them selves when working with photoswitches in close proximity to one another. Intermolecular interactions, such as aggregation, excitation quenching, low freevolume, as well as the poten tially much higher optical density of materials can drastically lower the overall photoresponse. Yet with proper macromo lecular and supramolecular design, functions can be achieved through the incorporation of photoswitches in a material that simply cannot be obtained by an isolated molecule on its own. Here, we highlight recent examples from the literature that have appeared during the past decade since our previous review in this journal, [5] with particular focus on the order of the photos witches in relation to their environment and its impact on mate rial properties and device performance.Conceptually, one can think about maximizing a photo switching unit's effect by giving it "order" with relation to its surrounding, in particular to other switching units (Figure 2). The lowest possible order is undoubtedly demonstrated by dis persing photochromic molecules in a bulk amorphous material. If aggregation of the photoswitches can be overcome, switching units are placed in random orientation to each other giving rise to a more or less isotropic material. Starting from this scenario of randomly distributed photochromic entities, one can think about providing order in two dimensions by placing Incorporating molecular photoswitches into various materials provides unique opportunities for controlling their properties and functions with high spatiotemporal resolution using remote optical stimuli. The great and largely still untapped potential of these photoresponsive systems has not yet been fully exploited due to the fundamental challenge...

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“…Die Synthese von o ‐ATE erfolgte zuerst durch eine Pd‐katalysierte Kreuzkupplung zwischen Cyclohexanon und 3‐Brom‐2‐methyl‐5‐[4‐(trifluormethyl)phenyl]thiophen, gefolgt von einer Umwandlung in das entsprechende Enoltriflat. Anschließend wurde die Guaiazulenylgruppe über eine Suzuki‐Kupplung mit 2‐Guaiazulenylboronsäurepinakolester eingeführt (siehe Schema S1) .…”

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Protonenvermittelter Ringschluss eines negativ photochromen, Azulen‐basierten Diarylethens

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Auf Protonen ansprechende photochrome Moleküle sind aufgrund ihrer Fähigkeit, auf nicht-invasive schnelle optische Stimuli zu reagieren, und wegen der ubiquitären Bedeutung von Protonierungs-und Deprotonierungsprozessen, sehr interessant. Üblicherweise befinden sich die sauren/basischen Stellen dieser Moleküle an Heteroatomen, die orthogonal zum photoaktiven p-Zentrum ausgerichtet sind. In dieser Arbeit wird Azulen, ein protonensensitiver reiner Kohlenwasserstoff, in das Gerüst eines Diarylethen-Photoschalters eingebaut. Dieser zeigt einen bisher ungekannten, protonenvermittelten, negativ photochromen Ringschluss. Veränderungen seiner optischen Eigenschaften durch Protonierung, sowohl in der offenen, als auch in der geschlossenen Form, sind viel ausgeprägter als die von Diarylethen-Photoschaltern mit Säure/Base-Gruppen auf Heteroatombasis. Das einzigartige Verhalten des neuen Photoschalters kann auf die direkte Protonierung seines p-Systems zurückgeführt werden, was sowohl durch 1 H-NMR als auch durch theoretische Berechnungen belegt wird. Unsere Ergebnisse zeigen das große Potenzial der Einbindung nicht-alternierender Kohlenwasserstoffe in photochrome Systeme für die Entwicklung von molekularen Schaltern, die auf unterschiedliche Stimuli reagieren.

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Sensitive Assays by Nucleophile-Induced Rearrangement of Photoactivated Diarylethenes

Cited by 46 publications

References 59 publications

Proton‐Gated Ring‐Closure of a Negative Photochromic Azulene‐Based Diarylethene

Proton‐Gated Ring‐Closure of a Negative Photochromic Azulene‐Based Diarylethene

Enlightening Materials with Photoswitches

Protonenvermittelter Ringschluss eines negativ photochromen, Azulen‐basierten Diarylethens

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