Surface Chemistry of the Molecular Solar Thermal Energy Storage System 2,3‐Dicyano‐Norbornadiene/Quadricyclane on Ni(111)

Molecular solar thermal (MOST) systems are a promising approach for the introduction of sustainable energy storage solutions. We investigated the feasibility of the dicyano‐substituted norbornadiene/quadricyclane molecule pair on Ni(111) for catalytic model studies. This derivatization is known to lead to a desired bathochromic shift of the absorption maximum of the parent compound. In our experiments further favorable properties were found: At low temperatures, both molecules adsorb intact without any dissociation. In situ temperature‐programmed HR‐XPS experiments reveal the conversion of (CN)(2)‐quadricyclane to (CN)(2)‐norbornadiene under energy release between 175 and 260 K. The absence of other surface species due to side reactions indicates full isomerization. Further heating leads to the decomposition of the molecular framework into smaller carbonaceous fragments above 290 K and finally to amorphous structures, carbide and nitride above 400 K. DFT calculations gave insights into the adsorption geometries. (CN)(2)‐norbornadiene is expected to interact stronger with the surface, with flat configurations being favorable. (CN)(2)‐quadricyclane exhibits smaller adsorption energies with negligible differences for flat and side‐on geometries. Simulated XP spectra are in good agreement with experimental findings further supporting the specific spectroscopic fingerprints for both valence isomers.