Photon Energy Storage in Strained Cyclic Hydrazones: Emerging Molecular Solar Thermal Energy Storage Compounds.

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.

Multistage Reversible Tg Photomodulation and Hardening of Hydrazone-Containing Polymers.

The glass transition temperature (Tg) of a series of polyacrylate- and polymethacrylate-based polymers having bistable hydrazone photoswitches as pendants increases upon photoisomerization. The ensuing photohardening of the polymeric network was corroborated using nanoindentation measurements. The bistability of the switch allowed us to lock-in and sustain multiple Tg values in the same polymeric material as a function of the hydrazone switch's Z/E isomer ratio, even at elevated temperatures.

Solution Phase and Surface Photoisomerization of a Hydrazone Switch with a Long Thermal Half-Life.

Photoswitches can be employed for various purposes, with the half-life being a crucial parameter to optimize for the desired application. The switching of a photochromic hydrazone functionalized with a C6 alkyl thiolate spacer (C6 HAT) was characterized on a number of metal surfaces. C6 HAT exhibits a half-life of 789 years in solution. Tip-enhanced Raman spectroscopy (TERS) was used to study the photoisomerization of the C6 HAT self-assembled monolayers (SAMs) on Au, Ag, and Cu surfaces. The unique spectroscopic signature of the E isomer at 1580 and 1730 cm-1 in TER spectra allowed for its discrimination from the Z isomer. It was found that C6 HAT switches on Au and Cu surfaces when irradiated with 415 nm; however, it cannot isomerize on Ag surfaces, unless higher energy light is used. Based on this finding, and supported by density functional theory calculations, we propose a substrate-mediated photoisomerization mechanism to explain the behavior of C6 HAT on these different metal surfaces. This insight into the hydrazone's switching mechanism on metal surfaces will contribute to the further exploitation of this new family photochromic compounds on metal surfaces. Finally, although we found that the thermal isomerization rate of C6 HAT drastically increases on metal surfaces, the thermal half-life is still 6.9 days on gold, which is longer than that of the majority of azobenzene-based systems.

Two-dimensional frameworks formed by pentagonal bipyramidal cobalt(ii) ions and hexacyanometallates: antiferromagnetic ordering, metamagnetism and slow magnetic relaxation.

We herein report the syntheses, structures, and magnetic properties of two isostructural two-dimensional (2D) coordination polymers based on a pentagonal bipyramidal CoII unit [Co(TODA)]2+ and two hexacyanometallates, namely [MIII(CN)6]2[CoII(TODA)]3·9H2O (M = Cr (1), Co (2), TODA = 1,4,10-trioxa-7,13-diazacyclopentadecane). Structure analyses show that both complexes have 2D honeycomb structures where the [Co(TODA)]2+ units are bridged by the [MIII(CN)6]3- groups through three cyano groups in the facial positions. Magnetic investigation reveals ferromagnetic coupling between the CrIII and CoII centres through cyanides in 1. Due to the antiferromagnetic interaction between the layers, compound 1 exhibits an antiferromagnetic ordering below 11.4 K, and shows a metamagnetic phase transition under an external dc field. Due to the disorder of the TODA ligands, compound 1 shows a spin glass behavior, which leads to slow magnetic relaxation in 1. A butterfly-shaped hysteresis loop at 1.8 K can be observed with a coercive field of 720 Oe, which is quite large for cyano-bridged Cr-Co molecular magnets. For compound 2 containing the diamagnetic [CoIII(CN)6]3- unit, field-induced slow magnetic relaxation was also verified, which makes compound 2 a rare example of an SIM assembled in a 2D network. An easy-plane magnetic anisotropy with a positive D value (29.9 cm-1 by PHI and 26.5 cm-1 by Anisofit2.0) was deduced for hepta-coordinated CoII centers. These results show the efficiency of the strategy of combining cyanometallates and pentagonal bipyramidal precursors for novel molecular magnetic materials.