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Photochem 2022, 2 702 Figure 4. Approximate 3D illustration of a ground-state (S0, blue) and excited (S1, red) energy landscape depicting the whole photoisomerization mechanism. Control of the back conversion reaction is crucial in providing energy at the right time. It is well known in these systems that the optimization of solar match and storage lifetime at the same time is challenging, because one property is improved at the expense of the other. However, a recent novel strategy defies this, wherein NBD molecules have an improved solar match, yet the storage time remains untouched. Chiefly, via the introduction of substituents in the ortho position, a substantial increase in back conversion ∆S* occurs, which comes from the steric interference of the side group of the parent molecule [55]. 3.2. Azobenzene Photoswitches Azobenzene is a chemical compound based on diazene (HN=NH), where both hydro- gens are substituted by a phenyl ring [56,57]. Azobenzene can be found either in a cis or trans conformation [58]. The trans to cis isomerization can be triggered by different stimuli such as irradiation with ultraviolet (UV) light [59], mechanical force [60], or an electrostatic stimulus [61,62]. Contrastingly, the cis to trans isomerization can be observed in dark conditions when applying heat owing to the thermodynamic stability of the trans isomer, although it can also be driven by visible light (see Figure 5a). The trans conformation assumes a planar structure with C2h symmetry [63,64], with a maximum distance of 9.0 Å between the most distant positions of the aromatic rings. On the other hand, the cis one adopts a non-planar conformation with C2 symmetry [65,66] and the end-to-end distance is reduced to 5.5 Å. The cis-isomer is not planar as a result of steric hindrance, and this causes the π-electron clouds of the aromatic rings to face each other, leading to a small dipolar moment in the molecule (μ ~3D) [67]. This ring’s disposition is also reflected in the proton nuclear magnetic resonance (1H-NMR) spectra. The shielding effect produced by the anisotropy of the π-electron cloud in the cis-isomer affects the signals, thus making them appear at a higher shift compared with the trans-isomer.PDF Image | Overview of Molecular Solar Thermal Energy Storage
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