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

ConspectusRenewable 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 toward the real-life application of MOST systems.