Organometallic sandwich complexes are versatile molecular systems that have been recently employed for single-molecule manipulation and spin sensing experiments. Among related organometallic compounds, the mixed-sandwich S = 1/2 complex (η8-cyclooctatetraene)(η5-cyclopentadienyl)titanium, here [CpTi(cot)], has attracted interest as a spin qubit because of the long coherence time. Here the structural and chemical properties of [CpTi(cot)] on Au(111) are investigated at the monolayer level by experimental and computational methods. Scanning tunneling microscopy suggests that adsorption occurs in two molecular orientations, lying and standing, with a 3:1 ratio. XPS data evidence that a fraction of the molecules undergo partial electron transfer to gold, while our computational analysis suggests that only the standing molecules experience charge delocalization toward the surface. Such a phenomenon depends on intermolecular interactions that stabilize the molecular packing in the monolayer. This orientation-dependent molecule-surface hybridization opens exciting perspectives for selective control of the molecule-substrate spin delocalization in hybrid interfaces.
Keywords: X-ray photoelectron spectroscopy; density functional theory; molecular packing; molecule/surface interactions; organometallic sandwich compounds; scanning tunneling microscopy.