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Photochem 2022, 2 710 the better the kinetic parameters, but, in contrast, an additional enhancement of system robustness is found with apolar solvents. Along the years, many different studies were performed to better understand and improve the DHA capabilities, aiming at a better performance. The effect of some vicinal chemical modifications over the photoisomerization from DHA to VHF was improved in the 90s, usually by adding some donor or acceptor electronic groups on para positions of the phenyl ring. This yields in a moderate modification of the photoreaction quantum yield, ranging from 0.6 to 0.3 when increasing the electron-withdrawing strength of the substituent in the para position [98]. More recently, some extensive computational analysis was performed for the screening of interesting new candidates. In this work [40], an impressively wide number of chemical modifications has been performed on DHA systems to tune some of their properties. The most relevant and effective ones are summarized in Figure 11, whereby the main interest was the substitutions in positions 1–3 and 7, according to the numbering seen below for DHA systems. Figure 11. Numbered positions and more relevant modifications in DHA structure, yielding some type of improvement. One of the first modifications was to check the importance of the CN groups in position 1 and, as can be expected according to the mechanism, the elimination of this strong electron-withdrawing group causes a lack of photoswitching capacity, proving that the strong electrophilic behavior of C1 is crucial in the charge transfer intermediate on the photochemical transformation. As the elimination lacks the photoisomerization, some interesting attempts to replace one of the CN with other EWGs were carried out [99]. To finalize, the substitution of one CN by an ethoxycarbonyl or carbamoyl group can maintain the photoswitching ability and enhance the energy storage capacity, increasing it by 0.05–0.1 MJ/kg on average, being a relevant increment, also considering the higher molecular weight. As counterpoint, the predicted ∆G is lower than that found in base DHA, facilitating the back conversion. Moreover, with these systems, the solvent dependence seems to be slightly lower, even being quite representative.PDF Image | Overview of Molecular Solar Thermal Energy Storage
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