Exploring the potential of fulvalene dimetals as platforms for molecular solar thermal energy storage: computations, syntheses, structures, kinetics, and catalysis.

A study of the scope and limitations of varying the ligand framework around the dinuclear core of FvRu2 in its function as a molecular solar thermal energy storage framework is presented. It includes DFT calculations probing the effect of substituents, other metals, and CO exchange for other ligands on ΔHstorage . Experimentally, the system is shown to be robust in as much as it tolerates a number of variations, except for the identity of the metal and certain substitution patterns.

Single-molecule-resolved structural changes induced by temperature and light in surface-bound organometallic molecules designed for energy storage.

We have used scanning tunneling microscopy, Auger electron spectroscopy, and density functional theory calculations to investigate thermal and photoinduced structural transitions in (fulvalene)tetracarbonyldiruthenium molecules (designed for light energy storage) on a Au(111) surface. We find that both the parent complex and the photoisomer exhibit striking thermally induced structural phase changes on Au(111), which we attribute to the loss of carbonyl ligands from the organometallic molecules. Density functional theory calculations support this conclusion.

Experimental realization of catalytic CH4 hydroxylation predicted for an iridium NNC pincer complex, demonstrating thermal, protic, and oxidant stability.

A discrete, air, protic, and thermally stable (NNC)Ir(III) pincer complex was synthesized that catalytically activates the CH bond of methane in trifluoroacetic acid; functionalization using NaIO4 and KIO3 gives the oxy-ester.