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The generally small Gibbs free energy difference between the Z and E isomers of hydrazone photoswitches has so far precluded their use in photon energy storing applications. Here, we report on a series of cyclic and acyclic hydrazones, which possess varied degrees of ring strain and, hence, stability of E isomers. The photoinduced isomerization and concurrent phase transition of the cyclic hydrazones from a crystalline to a liquid phase result in the storage of a large quantity of energy, comparable to that of azobenzene derivatives. We demonstrate that the macrocyclic photochrome design in combination with phase transition is a promising strategy for molecular solar thermal energy storage applications.

Azo-based photoswitches have shown promise as molecular solar-thermal (MOST) materials due to their ability to store energy in their metastable Z isomeric form. The energy is then released, in the form of heat, upon photoisomerization to the thermodynamically stable E form. However, obtaining a high energy density and recovering the stored energy with high efficiency requires the materials to be employed in the condensed phase and display a high degree of Z to E switching, both of which are challenging to engineer. Here, we show that arylazopyrazole motifs undergo efficient redox-induced Z to E switching in both the solution and the condensed phase to a higher completeness of switching than achieved photochemically. This redox-initiated pathway lowers the barrier of Z to E isomerization by 27 kJ/mol, while in the condensed phase, the efficiency of electrochemical switching is improved by over an order of magnitude relative to that in the solution state. The influence of the photoswitch's phase, electrical conductivity, and viscosity on the electrochemical switching in the condensed phase is reported, culminating in a set of design rules to facilitate further investigations. We anticipate the use of an alternative stimulus to light will facilitate the application of MOST materials in situations where phototriggered heat release is unachievable or inefficient, e.g., indoor or at night. Furthermore, exploiting the electrocatalytic mechanism, whereby a catalytic amount of charge triggers Z to E switching via a redox process, bypasses the need for fine tuning of the photoswitching chromophore to achieve complete Z to E switching, thus providing an alternative approach to photoswitch molecular design.

A series of compact azobenzene derivatives were investigated as phase-transition molecular solar thermal energy storage compounds that exhibit maximum energy storage densities around 300 J g -1 . The relative size and polarity of the functional groups on azobenzene were manifested to significantly influence the phase of isomers and their energy storage capacity.

Arylazopyrazole derivatives based on four core structures (4pzMe, 3pzH, 4pzH, and 4pzH-F2) and functionalized with a dodecanoate group were demonstrated to store thermal energy in their metastable Z isomer liquid phase and release the energy by optically triggered crystallization at -30 °C for the first time. Three heat storage-release schemes were discovered involving different activation methods (optical, thermal, or combined) for generating liquid-state Z isomers capable of storing thermal energy. Visible light irradiation induced the selective crystallization of the liquid phase via Z -to- E isomerization, and the latent heat stored in the liquid Z isomers was preserved for longer than 2 weeks unless optically triggered. Up to 92 kJ/mol of thermal energy was stored in the compounds, demonstrating remarkable thermal stability of Z isomers at high temperatures and liquid-phase stability at temperatures below 0 °C.

We use annular dark-field scanning transmission electron microscopy (ADF-STEM) to study how solution-deposited molecules bind to the edges and surface regions around nanopores in MoS 2 monolayers. Nanopores with clean atomically flat edges and controllable mean diameter were generated by time-dependent large-area electron beam exposure during an in situ heating process, ready for subsequent molecular attachment. An organic molecule was designed to have a dithiolane end group that binds to Mo-terminated sites and a ligand structure that incorporates a single transition metal atom (Pt) marker for ADF-STEM detection. Pt atoms were used to track molecular binding around zigzag edges of MoS 2 and to predict the orientations and conformations of molecules upon binding. We found that the molecules preferred to reside on the surface of the MoS 2 , pointing inward when attaching to the edge, rather than dangling out from the edge into free space, which is attributed to van der Waals interactions between the aromatic core of the molecule and the MoS 2 basal planes. These results help us understand the way solution-deposited single molecules attach to free-standing edges of 2D crystals and the influence of van der Waals forces in guiding molecular binding.

Isomerization behaviors of spiropyran derivatives in neat condensed phase were studied to understand their unusual phase transitions including cold-crystallization after extreme supercooling down to -50 °C. Compounds with different functional groups were compared, and the equilibrium between isomers at high temperatures was found to determine phase transitions.

Photoswitching behavior of individual organic molecules was imaged by annular dark-field scanning transmission electron microscopy (ADF-STEM) using a highly electron beam transparent graphene support. Photoswitching azobenzene derivatives with ligands at each end containing single transition-metal atoms (Pt) were designed (Pt-complex), and the distance between the strong ADF-STEM contrast from the two Pt atoms in each Pt-complex is used to track molecular length changes. UV irradiation was used to induce photoswitching of the Pt complex on graphene, and we show that the measured Pt-Pt distances within isolated molecules decrease from ∼2.1 nm to ∼1.4 nm, indicative of a trans-to- cis isomerization. Light illumination of the Pt-complex on the graphene support also caused their diffusion out from initial clusters to the surrounding area of graphene, indicating that the light-activated mobilization overcomes the intermolecular van der Waals interactions. This approach shows how individual isolated heavy metal atoms can be included as markers into complex molecules to track their structural changes using ADF-STEM on graphene supports, providing an effective method to study a diverse range of complex organic materials at the single molecule level.