Acid-catalysed thermal cycloreversion of a diarylethene: a potential way for triggered release of stored light energy?

Gurke, Johannes; Quick, Martin; Érnsting, N. P.; Hecht, Stefan

doi:10.1039/c6cc10182h

Cited by 53 publications

(49 citation statements)

References 21 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…DAEs are also potential materials for solar thermal energy storage; an acid was used to trigger thermal release of stored light energy upon thermal cycloreversion of a DAE …”

Section: Photoresponsive Materials and Nanostructuresmentioning

confidence: 99%

Recent Implementations of Molecular Photoswitches into Smart Materials and Biological Systems

Pianowski

2019

Chemistry A European J

285

226

View full text Add to dashboard Cite

Light is a nearly ideal stimulus for molecular systems. It delivers information encoded in the form of wavelengths and their intensities with high precision in space and time. Light is a mild trigger that does not permanently contaminate targeted samples. Its energy can be reversibly transformed into molecular motion, polarity, or flexibility changes. This leads to sophisticated functions at the supramolecular and macroscopic levels, from light‐triggered nanomaterials to photocontrol over biological systems. New methods and molecular adapters of light are reported almost daily. Recently reported applications of photoresponsive systems, particularly azobenzenes, spiropyrans, diarylethenes, and indigoids, for smart materials and photocontrol of biological setups are described herein with the aim to demonstrate that the 21st century has become the Age of Enlightenment—“Le siècle des Lumières”—in molecular sciences.

show abstract

“…DAEs are also potential materials for solar thermal energy storage; an acid was used to trigger thermal release of stored light energy upon thermal cycloreversion of a DAE …”

Section: Photoresponsive Materials and Nanostructuresmentioning

confidence: 99%

Recent Implementations of Molecular Photoswitches into Smart Materials and Biological Systems

Pianowski

2019

Chemistry A European J

285

226

View full text Add to dashboard Cite

show abstract

“…The basic physical effect responsible for this surprising feature is the delocalized nature of the polaritonic states obtained under collective strong coupling, which require a treatment of the whole collection of molecules as a single polaritonic supermolecule. For the specific model studied here, this strategy could resolve one of the main problems of solar energy storage; that is, how to efficiently retrieve the stored energy from molecules that are designed for the opposite purpose, i.e., for storing energy very efficiently under normal conditions [20,21]. By reversibly bringing the system into strong coupling (e.g., through a moving mirror that brings the cavity into and out of resonance), one could thus trigger the release of the stored energy through absorption of a single ambient photon.…”

Section: Prl 119 136001 (2017) P H Y S I C a L R E V I E W L E T T Ementioning

confidence: 99%

“…We thus investigate a class of reactions that release energy, i.e., where the initial starting state after absorption of a photon has higher energy than the final state, in which all involved molecules have undergone a reaction. We focus on a class of model molecules with a structure as proposed for use in solar energy storage [19][20][21], described within a simplified model treating a single reaction coordinate, as shown in Fig. 1(a).…”

mentioning

confidence: 99%

Inducing Multiple Reactions with a Single Photon

Ruggenthaler

2017

Physics

View full text Add to dashboard Cite

The second law of photochemistry states that, in most cases, no more than one molecule is activated for an excited-state reaction for each photon absorbed by a collection of molecules. In this Letter, we demonstrate that it is possible to trigger a many-molecule reaction using only one photon by strongly coupling the molecular ensemble to a confined light mode. The collective nature of the resulting hybrid states of the system (the so-called polaritons) leads to the formation of a polaritonic "supermolecule" involving the degrees of freedom of all molecules, opening a reaction path on which all involved molecules undergo a chemical transformation. We theoretically investigate the system conditions for this effect to take place and be enhanced. DOI: 10.1103/PhysRevLett.119.136001 Photochemical reactions underlie many essential biological functions, such as vision or photosynthesis. In this context, the second law of photochemistry (also known as the Stark-Einstein law) states that "one quantum of light is absorbed per molecule of absorbing and reacting substance" [1]. This means that the quantum yield ϕ ¼ N prod =N phot of the reaction, which describes the percentage of molecules that end up in the desired reaction product per absorbed photon, has a maximum value of 1. This limit can be overcome in some specific cases, such as in photochemically induced chain reactions [2-4], or in systems that support singlet fission to create multiple triplet excitons (and thus electron-hole pairs) in solar cells [5,6].Polaritonic chemistry, i.e., the potential to manipulate chemical structure and reactions through the formation of polaritons (hybrid light-matter states) was experimentally demonstrated in 2012 [7], and has become a topic of intense experimental and theoretical research in the past few years [8][9][10][11][12][13][14][15][16][17][18]. However, existing applications and proposals have been limited to enhancing or suppressing the rates of single-molecule reactions. In this Letter we demonstrate a novel and general approach to circumvent the StarkEinstein law by exploiting the collective nature of polaritons formed by bringing a collection of molecules into strong coupling with a confined light mode. We show that this can allow many molecules to undergo a photochemical reaction after excitation by just a single photon. In contrast to conventional chain reactions, this polaritonic reaction does not rely on a near-resonant energy transfer condition between the excited stable and metastable ground state in the molecule. Our finding illustrates how polaritonic chemistry can open fundamentally new pathways that allow for reactions that are not present in the uncoupled system, and thus possesses the potential to unlock a new class of collective reactions.The mechanism we introduce relies on the delocalized character of the hybrid light-matter excitations (polaritons) formed under strong coupling (SC), which conceptually leads to the formation of a single "supermolecule" involving all the molecules as well as the trapp...

show abstract

“…Im Laufe der Untersuchungen fiel eine nicht erwartete Reaktion eines der Diastereomere gegenüber Veränderung der chemischen Umgebung auf:I nteressanterweise führte Ansäuern des Mediums,w as typerweise zur vereinfachten Ionisierung fürd ie UPLC-Analyse dient, zur sofortigen thermischen Ringçffnung von Ma aj jo or r-1 c bei 25 8 8C, während Mi in no or r-1 c unverändert blieb.Obwohl bereits einige Berichte über protoneninduzierte Ringçffnungen von DAEs erschienen, [20]…”

unclassified

“…Da Mi in no or r-1cstabiler als Ma aj jo or r-1 c ist, ist die Reaktionsenergie mit TFA fürl etzteres deutlich geringer (15,6 kJ mol À1 vs.43,9 kJ mol À1 für Mi in no or r-1 c,s iehe Abbildung 3a). Angesichts einiger Berichte über die Protonierung als mçglichen Pfad zur thermischen Ringçffnung von Diarylethenen[20] liefern diese Berechnungsergebnisse eine überzeugende Erklärung fürd ie diastereoselektive thermische Ringçffnung von Ma aj jo or r-1 c, die in sauren Medien beobachtet wurde.Durch die Implementierung von Stereoinformationeni n das Rückgrat eines Diarylethens konnten wir einen effizienten Chiralitätstransfer bei der Photocyclisierung nachweisen. Noch wichtiger ist, dass das resultierende Diastereomerenverhältnis einfach durch ¾nderung der Bestrahlungsbedingungen oder der chemischen Umgebung umgekehrt werden kann.…”

unclassified

Externe Umkehr eines Chiralitätstransfers im Photoschalter

et al. 2019

Self Cite

View full text Add to dashboard Cite

Der Transfer von Stereoinformation ist das Herzstück asymmetrischer Reaktionen. Durchd ie Integration des natürlichen Monoterpens l-Menthon in das Rückgrat eines Diarylethens konnte ein effizienter Chiralitätstransfer bei der Photocyclisierung erreicht werden, was zur bevorzugten Bildung eines geschlossenen Hauptisomers mit einem Diastereomerenverhältnis (d.r.) von 85:15 führte.N och stärker hervorzuheben ist allerdings,d ass die Diastereoselektivitätd es Ringschlusses vollständig umgekehrt werden kann, indem die chemische Umgebung oder die Bestrahlungsbedingungen verändert werden. Infolgedessen konnte selektiv das weniger favorisierte geschlossene Isomer mit bemerkenswerten d.r.-Werten von > 99:1 bzw.7 4:26 akkumuliert werden. Berechnungen zeigen,d ass eine Stabilitätsinversion nachd er Photocyclisierung die Grundlage fürd ie beobachtete beispiellose Kontrolle der Diastereoselektivitäti st.

show abstract

Acid-catalysed thermal cycloreversion of a diarylethene: a potential way for triggered release of stored light energy?

Cited by 53 publications

References 21 publications

Recent Implementations of Molecular Photoswitches into Smart Materials and Biological Systems

Recent Implementations of Molecular Photoswitches into Smart Materials and Biological Systems

Inducing Multiple Reactions with a Single Photon

Externe Umkehr eines Chiralitätstransfers im Photoschalter

Contact Info

Product

Resources

About