Soft-landing isolation of gas-phase-synthesized transition metal-benzene complexes into a fluorinated self-assembled monolayer matrix

Gas-phase-synthesized chromium-benzene 1:2 sandwich cation complexes [Cr⁺(benzene)²] were soft-landed on a self-assembled monolayer (SAM) of fluorinated alkanethiol (C₁₀F-SAM) at a hyperthermal collision energy of ∼20 eV. The adsorption properties and thermal stability of the soft-landed complexes were studied with infrared reflection absorption spectroscopy (IRAS) and temperature-programmed desorption (TPD). The landed complexes were neutralized due to charge transfer from the SAM substrate, but their native sandwich structure remained intact. The hyperthermal collision event resulted in the penetration of the incoming complexes into the C₁₀F-SAM matrix. The embedded complexes then tended to orient their molecular axes approximately along the surface normal. This orientational preference is measurably different from that of complexes isolated in alkanethiol SAM matrices, a discrepancy that might be caused by a repulsive interaction between the n cloud of the capping benzene rings of the complex and the side-chain CF₂ groups of the fluorocarbon chains in the C₁₀F-SAM matrix. The thermal desorption study showed that the complexes supported inside the C₁₀F-SAM could resist thermal desorption until the high-temperature region of ∼320 K, a persistence revealing a large desorption activation energy (∼190 kJ/mol).