Tuning the dihydroazulene – vinylheptafulvene couple for storage of solar energy

Nielsen, Mogens Brøndsted; Ree, Nicolai; Mikkelsen, Kurt V.; Cacciarini, Martina

doi:10.1070/rcr4944

Cited by 57 publications

(37 citation statements)

References 52 publications

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“…And maybe more problematic, these molecules have rather complicated substitution patterns. There are today synthetic protocols available for functionalizing selectively at positions 1, 2, 3 and 7 (and in part position 6) of DHA, (Nielsen et al, 2020) but so far these protocols have only been used to introduce substituents efficiently at maximum three positions (see SI for further synthetic considerations). So new synthetic protocols need to be developed for introducing substituents around the entire DHA core, and some suitable protecting groups need to be installed, for example to allow both amino and aldehyde functionalities in the same molecule.…”

Section: Discussionmentioning

confidence: 99%

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High throughput virtual screening of 230 billion molecular solar heat battery candidates

Koerstz

Christensen

Mikkelsen

et al. 2021

PeerJ Physical Chemistry

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The dihydroazulene/vinylheptafulvene (DHA/VHF) thermocouple is a promising candidate for thermal heat batteries that absorb and store solar energy as chemical energy without the need for insulation. However, in order to be viable the energy storage capacity and lifetime of the high energy form (i.e., the free energy barrier to the back reaction) of the canonical parent compound must be increased significantly to be of practical use. We use semiempirical quantum chemical methods, machine learning, and density functional theory to virtually screen over 230 billion substituted DHA molecules to identify promising candidates. We identify a molecule with a predicted energy density of 0.38 kJ/g, which is significantly larger than the 0.14 kJ/g computed for the parent compound. The free energy barrier to the back reaction is 11 kJ/mol higher than the parent compound, which should correspond to a half-life of about 10 days—4 months. This is considerably longer than the 3–39 h (depending on solvent) observed for the parent compound and sufficiently long for many practical applications. Our paper makes two main important contributions: (1) a novel and generally applicable methodological approach that makes screening of huge libraries for properties involving chemical reactivity with modest computational resources, and (2) a clear demonstration that the storage capacity of the DHA/VHF thermocouple cannot be increased to >0.5 kJ/g by combining simple substituents.

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Section: Discussionmentioning

confidence: 99%

“…Therefore finding solutions for storing solar energy is one of the major challenges for a sustainable society. One approach is to employ light-induced isomerization of photoactive molecules (Moth-Poulsen, 2013;Nielsen et al, 2020) as exemplified by the dihydroazulene/vinylheptafulvene (DHA/VHF) thermocouple in Fig. 1.…”

Section: Introductionmentioning

confidence: 99%

High throughput virtual screening of 230 billion molecular solar heat battery candidates

Koerstz

Christensen

Mikkelsen

et al. 2021

PeerJ Physical Chemistry

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show abstract

“…And maybe more problematic, these molecules have rather complicated substitution patterns. There are today synthetic protocols available for functionalizing selectively at positions 1, 2, 3, and 7 (and in part position 6) of DHA, [2] but so far these protocols have only been used to introduce substituents efficiently at maximum three positions (see SI for further synthetic considerations). So new synthetic protocols need to be developed for introducing substituents around the entire DHA core, and some suitable protecting groups need to be installed, for example to allow both amino and aldehyde functionalities in the same molecule.…”

Section: Discussionmentioning

confidence: 99%

“…Therefore finding solutions for storing solar energy is one of the major challenges for a sustainable society. One approach is to employ light-induced isomerization of photoactive molecules [1,2] as exemplified by the DHA/VHF thermocouple in Figure 1. Upon irradiation, a molecule is converted to a high-energy photo-isomer and upon a certain stimulus, the high-energy isomer returns to the original molecule, and the excess energy is released as heat.…”

Section: Introductionmentioning

confidence: 99%

Peer Review #3 of "High throughput virtual screening of 230 billion molecular solar heat battery candidates (v0.1)"

Jinich¹

2021

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The dihydroazulene/vinylheptafulvene (DHA/VHF) thermocouple is a promising candidate for thermal heat batteries that absorb and store solar energy as chemical energy without the need for insulation. However, in order to be viable the energy storage capacity and lifetime of the high energy form (i.e. the free energy barrier to the back reaction) of the canonical parent compound must be increased significantly to be of practical use. We use semiempirical quantum chemical methods, machine learning, and density functional theory to virtually screen over 230 billion substituted DHA molecules to identify promising candidates. We identify a molecule with a predicted energy density of 0.38 kJ/g, which is significantly larger than the 0.14 kJ/g computed for the parent compound. The free energy barrier to the back reaction is 11 kJ/mol higher than the parent compound, which should correspond to a half-life of about 10 days -4 months. This is considerably longer than the 3-39 hours (depending on solvent) observed for the parent compound and sufficiently long for many practical applications. Our paper makes two main important contributions: 1) a novel and generally applicable methodological approach that makes screening of huge libraries for properties involving chemical reactivity with modest computational resources, and 2) a clear demonstration that the storage capacity of the DHA/VHF thermocouple cannot be increased to >0.5 kJ/g by combining simple substituents.

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“…Several photochromic motifs have been proposed for MOST systems including (fulvalene) tetracarbonyldiruthenium, 8 − 10 azobenzene, 11 − 14 dihydroazulene, 15 − 17 and arguably the most studied system, norbornadiene (NBD). 2 , 3 , 18 − 27 NBD and its derivatives are appealing because of their high isomerization quantum yields for formation of the metastable quadricyclane (QC), low molecular weight, stability of the QC isomer over time, high fatigue resistance, and facile external triggering of the back-reaction from QC to NBD via thermal activation (see Figure 1 ).…”

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confidence: 99%

Photo- and Collision-Induced Isomerization of a Charge-Tagged Norbornadiene–Quadricyclane System

Jacovella

Carrascosa

Buntine

et al. 2020

J. Phys. Chem. Lett.

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Molecular photoswitches based on the norbornadiene–quadricylane (NBD–QC) couple have been proposed as key elements of molecular solar thermal energy storage schemes. To characterize the intrinsic properties of such systems, reversible isomerization of a charge-tagged NBD–QC carboxylate couple is investigated in a tandem ion mobility mass spectrometer, using light to induce intramolecular [2 + 2] cycloaddition of NBD carboxylate to form the QC carboxylate and driving the back reaction with molecular collisions. The NBD carboxylate photoisomerization action spectrum recorded by monitoring the QC carboxylate photoisomer extends from 290 to 360 nm with a maximum at 315 nm, and in the longer wavelength region resembles the NBD carboxylate absorption spectrum recorded in solution. Key structural and photochemical properties of the NBD–QC carboxylate system, including the gas-phase absorption spectrum and the energy storage capacity, are determined through computational studies using density functional theory.

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Tuning the dihydroazulene – vinylheptafulvene couple for storage of solar energy

Cited by 57 publications

References 52 publications

High throughput virtual screening of 230 billion molecular solar heat battery candidates

High throughput virtual screening of 230 billion molecular solar heat battery candidates

Peer Review #3 of "High throughput virtual screening of 230 billion molecular solar heat battery candidates (v0.1)"

Photo- and Collision-Induced Isomerization of a Charge-Tagged Norbornadiene–Quadricyclane System

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