Solar energy conversion and solar energy storage are key challenges for a future society with limited access to fossil fuels. Certain compounds that undergo light-induced isomerisation to a metastable isomer can be used for storage of solar energy, so-called molecular solar thermal systems. Exposing the compound to sun light will generate a high energy photoisomer that can be stored. When energy is needed, the photoisomer can be catalytically converted back to the parent compound, releasing the excess energy as heat. This Letter gives examples of selected molecular solar thermal systems found in the literature. The focus of the Letter is on examples where molecular design has been used to improve the performance of the molecules, and as such it may serve as an inspiration for future design. The selected examples cover five widely studied systems, notably: anthracenes, stilbenes, azobenzenes, tetracarbonyl-fulvalene-diruthenium compounds and norbornadienes

CO ₂ conversion to small bio-molecules on greigite minerals under room temperature and pressure.

A hybrid solar energy system consisting of a molecular solar thermal energy storage system (MOST) combined with a solar water heating system (SWH) is presented. The MOST chemical energy storage system is based on norbornadiene–quadricyclane derivatives allowing for conversion of solar energy into stored chemical energy at up to 103 kJ mol⁻¹ (396 kJ kg⁻¹). It is demonstrated that 1.1% of incoming solar energy can be stored in the chemical system without significantly compromising the efficiency of the solar water heating system, leading to efficiencies of combined solar water heating and solar energy storage of up to 80%. Moreover, prospects for future improvement and possible applications are discussed.

Efficient solar energy storage is a key challenge in striving toward a sustainable future. For this reason, molecules capable of solar energy storage and release through valence isomerization, for so‐called molecular solar thermal energy storage (MOST), have been investigated. Energy storage by photoconversion of the dihydroazulene/vinylheptafulvene (DHA/VHF) photothermal couple has been evaluated. The robust nature of this system is determined through multiple energy storage and release cycles at elevated temperatures in three different solvents. In a nonpolar solvent such as toluene, the DHA/VHF system can be cycled more than 70 times with less than 0.01 % degradation per cycle. Moreover, the [Cu(CH₃CN)₄]PF₆‐catalyzed conversion of VHF into DHA was demonstrated in a flow reactor. The performance of the DHA/VHF couple was also evaluated in prototype photoconversion devices, both in the laboratory by using a flow chip under simulated sunlight and under outdoor conditions by using a parabolic mirror. Device experiments demonstrated a solar energy storage efficiency of up to 0.13 % in the chip device and up to 0.02 % in the parabolic collector. Avenues for future improvements and optimization of the system are also discussed.

Square-planar nickel bis(dithiocarbamate) complexes, [Ni(S₂CNR₂)₂], have been prepared and utilised as single source precursors to nanoparticulate nickel sulfides. While they are stable in the solid-state to around 300 °C, heating in oleylamine at 230 °C, 5 mM solutions afford pure α-NiS, where the outcome is independent of the substituents. DFT calculations show an electronic effect rather than steric hindrance influences the resulting particle size. Decomposition of the iso-butyl derivative, [Ni(S₂CNⁱBu₂)₂], has been studied in detail. There is a temperature-dependence of the phase of the nickel sulfide formed. At low temperatures (150 °C), pure α-NiS is formed. Upon raising the temperature, increasing amounts of β-NiS are produced and at 280 °C this is formed in pure form. A range of concentrations (from 5–50 mM) was also investigated at 180 °C and while in all cases pure α-NiS was formed, particle sizes varied significantly. Thus at low concentrations average particle sizes were ca. 100 nm, but at higher concentrations they increased to ca. 150 nm. The addition of two equivalents of tetra-iso-butyl thiuram disulfide, (ⁱBu₂NCS₂)₂, to the decomposition mixture was found to influence the material formed. At 230 °C and above, α-NiS was generated, in contrast to the results found without added thiuram disulfide, suggesting that addition of (ⁱBu₂NCS₂)₂ stabilises the metastable α-NiS phase. At low temperatures (150–180 °C) and concentrations (5 mM), mixtures of α-NiS and Ni₃S₄, result. A growing proportion of Ni₃S₄ is noted upon increasing precursor concentration to 10 mM. At 20 mM a metastable phase of nickel sulfide, NiS₂ is formed and as the concentration is increased, α-NiS appears alongside NiS₂. Reasons for these variations are discussed.