Mechanism of Thermal Reversal of the (Fulvalene)tetracarbonyldiruthenium Photoisomerization: Toward Molecular Solar–Thermal Energy Storage

In the currently intensifying quest to harness solar energy for the powering of our planet, most efforts are centered around photoinduced generic charge separation, such as in photovoltaics, water splitting, other small molecule activation, and biologically inspired photosynthetic systems. In contrast, direct collection of heat from sunlight has received much less diversified attention, its bulk devoted to the development of concentrating solar thermal power plants, in which mirrors are used to focus the sun beam on an appropriate heat transfer material. An attractive alternative strategy would be to trap solar energy in the form of chemical bonds, ideally through the photoconversion of a suitable molecule to a higher energy isomer, which, in turn, would release the stored energy by thermal reversal. Such a system would encompass the essential elements of a rechargeable heat battery, with its inherent advantages of storage, transportability, and use on demand. The underlying concept has been explored extensively with organic molecules (such as the norbornadiene-quadricyclane cycle), often in the context of developing photoswitches. On the other hand, organometallic complexes have remained relatively obscure in this capacity, despite a number of advantages, including expanded structural tunability and generally favorable electronic absorption regimes. A highly promising organometallic system is the previously reported, robust photo-thermal fulvalene (Fv) diruthenium couple 1 {l_reversible} 2 (Scheme 1). However, although reversible and moderately efficient, lack of a full, detailed atom-scale understanding of its key conversion and storage mechanisms have limited our ability to improve on its performance or identify optimal variants, such as substituents on the Fv, ligands other than CO, and alternative metals. Here we present a theoretical investigation, in conjunction with corroborating experiments, of the mechanism for the heat releasing step of 2 {yields} 1 and its Fe (4) and Os (6) relatives. The results of the combined study has enabled a rigorous interpretation of earlier and new experimental measurements and paint a surprising picture. First-principles calculations were employed based on spin unrestricted density functional theory (DFT) with a non-empirical gradient corrected exchange-correlation functional. Ultrasoft pseudopotentials were used to describe the valence-core interactions of electrons, including scalar relativistic effects of the core. Wavefunctions and charge densities were expanded in plane waves with kinetic energies up to 25 and 200 Rydberg, respectively. Reaction pathways were delineated with the string method, as implemented within the Car-Parrinello approach. This method allows for the efficient determination of the minimum energy path (MEP) of atomistic transitions and thus also saddle points (transition states, TSs), which are the energy maxima along the MEP. All geometries were optimized until all forces on the atoms were less than 0.02 eV/{angstrom}. The calculated structures of 1 and 2 were in good agreement with their experimental counterparts.