The development of solar energy can potentially meet the growing requirements for a global energy system beyond fossil fuels, but necessitates new scalable technologies for solar energy storage.

Norbornadiene-quadricyclane (NBD-QC) photoswitches are candidates for applications in solar thermal energy storage. Functionally, they rely on an intramolecular [2+2] cycloaddition reaction, which couples the S landscape on the NBD side to the S landscape on the QC side of the reaction and vice-versa. This commonly results in an unfavourable correlation between the first absorption maximum and the barrier for thermal back-conversion. This work demonstrates that this correlation can be counteracted by using steric repulsion to hamper the rotational motion of the side groups along the back-conversion path. It is shown that this modification reduces the correlation between the effective back-conversion barrier and the first absorption maximum and also increases the back-conversion entropy. The resulting molecules exhibit exceptionally long half-lives for their metastable forms without significantly affecting other properties, most notably solar spectrum match and storage density.

Molecular photoswitches can be used for solar thermal energy storage by photoisomerization into high-energy, meta-stable isomers; we present a molecular design strategy leading to photoswitches with high energy densities and long storage times. High measured energy densities of up to 559 kJ kg−1 (155 Wh kg−1), long storage lifetimes up to 48.5 days, and high quantum yields of conversion of up to 94% per subunit are demonstrated in norbornadiene/quadricyclane (NBD/QC) photo-/thermoswitch couples incorporated into dimeric and trimeric structures. By changing the linker unit between the NBD units, we can at the same time fine-tune light-harvesting and energy densities of the dimers and trimers so that they exceed those of their monomeric analogs. These new oligomers thereby meet several of the criteria to be met for an optimum molecule to ultimately enter actual devices being able to undergo closed cycles of solar light-harvesting, energy storage, and heat release.

Charge transport by tunnelling is one of the most ubiquitous elementary processes in nature. Small structural changes in a molecular junction can lead to significant difference in the single-molecule electronic properties, offering a tremendous opportunity to examine a reaction on the single-molecule scale by monitoring the conductance changes. Here, we explore the potential of the single-molecule break junction technique in the detection of photo-thermal reaction processes of a photochromic dihydroazulene/vinylheptafulvene system. Statistical analysis of the break junction experiments provides a quantitative approach for probing the reaction kinetics and reversibility, including the occurrence of isomerization during the reaction. The product ratios observed when switching the system in the junction does not follow those observed in solution studies (both experiment and theory), suggesting that the junction environment was perturbing the process significantly. This study opens the possibility of using nano-structured environments like molecular junctions to tailor product ratios in chemical reactions.

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.