Turn-off mode fluorescent norbornadiene-based photoswitches

Tebikachew, Behabitu Ergette; Edhborg, Fredrik; Kann, Nina; Albinsson, Bo; Moth‐Poulsen, Kasper

doi:10.1039/c8cp04329a

Cited by 18 publications

(35 citation statements)

References 46 publications

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“…(iii) Heat release: after efficient storage of the energy over time, the energy can be released when the photoisomer back converts to the parent molecule; the process can be triggered by an external stimulus, such as a catalyst, 3 electrochemistry, 27 heat, or light. 28 − 30 (iv) Stability and availability: the system should be simple to prepare, economically feasible, and robust over extended periods and many cycles. All the properties together constitute a complex challenge for molecular design ( Figure 1 ).…”

Section: Introductionmentioning

confidence: 99%

Engineering of Norbornadiene/Quadricyclane Photoswitches for Molecular Solar Thermal Energy Storage Applications

2020

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Conspectus Renewable energy resources are mostly intermittent and not evenly distributed geographically; for this reason, the development of new technologies for energy storage is in high demand. Molecules that undergo photoinduced isomerization reactions that are capable of absorbing light, storing it as chemical energy, and releasing it as thermal energy on demand are referred to as molecular solar thermal energy storage (MOST) or solar thermal fuels (STF). Such molecules offer a promising solution for solar energy storage applications. Different molecular systems have been investigated for MOST applications, such as norbornadienes, azobenzenes, stilbenes, ruthenium derivatives, anthracenes, and dihydroazulenes. The polycyclic strained molecule norbornadiene (NBD), which photoconverts to quadricyclane (QC), is of great interest because it has a high energy storage density and the potential to store energy for a very long time. Unsubstituted norbornadiene has some limitations in this regard, such as poor solar spectrum match and low quantum yield. In the past decade, our group has developed and tested new NBD systems with improved characteristics. Moreover, we have demonstrated their function in laboratory-scale test devices for solar energy harnessing, storage, and release. This Account describes the most impactful recent findings on how to engineer key properties of the NBD/QC system (photochemistry, energy storage, heat release, stability, and synthesis) as well as examples of test devices for solar energy capture and heat release. While it was known that introducing donor–acceptor groups allows for a red-shifted absorption that better matches the solar spectrum, we managed to introduce donor and acceptor groups with very low molecular weight, which allowed for an unprecedented solar spectrum match combined with high energy density. Strategic steric hindrance in some of these systems dramatically increases the storage time of the photoisomer QC, and dimeric systems have independent energies barriers that lead to an improved solar spectrum match, prolonged storage times, and higher energy densities. These discoveries offer a toolbox of possible chemical modifications that can be used to tune the properties of NBD/QC systems and make them suitable for the desired applications, which can be useful for anyone wanting to take on the challenge of designing efficient MOST systems. Several test devices have been built, for example, a hybrid MOST device that stores sunlight energy and heat water at the same time. Moreover, we developed a device for monitoring catalyzed QC to NBD conversion resulting in the possibility to quantify a significant macroscopic heat generation. Finally, we tested different formulations of polymeric composites that can absorb light during the day and release the energy as heat during the night for possible use in future window coating applications. These lab-scale realizations are formative and contribute to pushing the field forward towar...

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Section: Introductionmentioning

confidence: 99%

Engineering of Norbornadiene/Quadricyclane Photoswitches for Molecular Solar Thermal Energy Storage Applications

2020

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“…This has been shown in molecular solar thermal (MOST) storage [3] also referred to as solar thermal fuel (STF). [7] Molecular photoswitch systems that have been studied for MOST include azobenzenes, [4,8] tetracarbonylfulvalenediruthenium complexes, [3,9] dihydroazulenes, [10] and NBDs. This metastable species can be stored until the energy is released as heat, leading to the reformation of the parent form.…”

Section: Doi: 101002/advs201900367mentioning

confidence: 99%

“…Such heat release can be prompted by heating or even occur under ambient conditions depending upon the storage life time ( t 1/2 ) of the high‐energy isomer. Moreover, this process has been shown to occur through a stimulus such as a heterogeneous catalyst, electric potential, or light . Molecular photoswitch systems that have been studied for MOST include azobenzenes, tetracarbonylfulvalenediruthenium complexes, dihydroazulenes, and NBDs…”

Section: Introductionmentioning

confidence: 99%

“…One solution is to address both light harnessing and storage in a combined technology. [7] Molecular photoswitch systems that have been studied for MOST include azobenzenes, [4,8] tetracarbonylfulvalenediruthenium complexes, [3,9] dihydroazulenes, [10] and NBDs. [4] Here, energy can be stored in a molecular photoswitch through irradiation under sunlight, resulting in the formation of a high energy isomer.…”

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Solar Energy Storage by Molecular Norbornadiene–Quadricyclane Photoswitches: Polymer Film Devices

et al. 2019

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Devices that can capture and convert sunlight into stored chemical energy are attractive candidates for future energy technologies. A general challenge is to combine efficient solar energy capture with high energy densities and energy storage time into a processable composite for device application. Here, norbornadiene (NBD)–quadricyclane (QC) molecular photoswitches are embedded into polymer matrices, with possible applications in energy storing coatings. The NBD–QC photoswitches that are capable of absorbing sunlight with estimated solar energy storage efficiencies of up to 3.8% combined with attractive energy storage densities of up to 0.48 MJ kg −1 . The combination of donor and acceptor units leads to an improved solar spectrum match with an onset of absorption of up to 529 nm and a lifetime ( t 1/2 ) of up to 10 months. The NBD–QC systems with properties matched to a daily energy storage cycle are further investigated in the solid state by embedding the molecules into a series of polymer matrices revealing that polystyrene is the preferred choice of matrix. These polymer devices, which can absorb sunlight and over a daily cycle release the energy as heat, are investigated for their cyclability, showing multicycle reusability with limited degradation that might allow them to be applied as window laminates.

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“… 23 , 24 Quadricyclane to norbornadiene photoisomerization in the newer generations of derivatives with red-shifted absorption is, however, extremely rare. 40 Despite this fact, we decided to irradiate QC with light at 310 nm, and to our surprise it readily and almost completely converted to NBD. This feature is of great interest, since it allows conversion of QC to NBD on a much shorter time scale than the thermal process.…”

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Three-Input Molecular Keypad Lock Based on a Norbornadiene–Quadricyclane Photoswitch

Dreos

Wang

Tebikachew

et al. 2018

J. Phys. Chem. Lett.

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The photo- and acidochromic properties of a new generation norbornadiene derivative have been harnessed for the realization of a three-input keypad lock, where a specific sequence of inputs induces a unique output. Reversible quadricyclane/norbornadiene photoisomerization is reported, and this rare feature allows the first example of a norbornadiene-based molecular logic system. The function of this system is clearly rationalized in terms of the interconversion scheme and the absorption spectra of the involved species.

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Turn-off mode fluorescent norbornadiene-based photoswitches

Abstract: To explore the potential of negative photochromic molecules for possible optical memory storage applications, we have here synthesized and studied a series of four norbornadiene–quadricyclane (NBD–QC) photoswitching molecules.

Cited by 18 publications

References 46 publications

Engineering of Norbornadiene/Quadricyclane Photoswitches for Molecular Solar Thermal Energy Storage Applications

Engineering of Norbornadiene/Quadricyclane Photoswitches for Molecular Solar Thermal Energy Storage Applications

Solar Energy Storage by Molecular Norbornadiene–Quadricyclane Photoswitches: Polymer Film Devices

Three-Input Molecular Keypad Lock Based on a Norbornadiene–Quadricyclane Photoswitch

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