Although physisorption is a widely occurring mechanism of bonding at the organic/metal interface, contradictory interpretations of this phenomenon are often reported. Photoemission and X-ray absorption spectroscopy investigations of nanorods of a substituted pentacene, 2,3,9,10-tetrafluoropentacene, deposited on gold single crystals reveal to be fundamental to identify the bonding mechanisms. We find fingerprints of a fractional charge transfer from the clean metal substrate to the physisorbed molecules. This phenomenon is unambiguously recognizable by a non-rigid shift of the core-level main lines while the occupied states at the interface stay mostly unperturbed, and the unoccupied states experience pronounced changes.The experimental results are corroborated by first-principles calculations.

We evidence the intercorrelation of electronic, structural, and morphological properties in nanorods of a substituted fluorine-based pentacene, 2,3,9,10-tetrafluoropentacene, deposited on gold single crystals by using photoemission and X-ray absorption spectroscopy investigations. Our investigations show changes in the XPS spectroscopy lines, and NEXAFS features correlate with the specific structure of the assemblies and their morphology. Consequently, the chemical structure affects not only the molecular electronic structure and the way the molecules assemble in a film but also the film morphology leading to specific thin film electronic properties.

Aiming at future technological applications, we describe the interface and the thin film processes of a pyrene-substituted nitronyl nitroxide radical deposited on Al2O3(11-20) single crystals. Electronic properties, chemical environment at the interface, and morphology of the thin films have been investigated by a multitechnique approach. Spectroscopic and morphologic analyses indicate a Stranski-Krastanov growth mode and weak physisorption of the molecules on the surface. The deposition does not affect the paramagnetic character of the molecules. The results presented in this paper show not only that the investigated system is a promising candidate as a model for understanding thin film processes in purely organic-based magnets, but its characteristics are worth its future use in electronics, because the radical character of the molecules is completely preserved in the thin films.

I n the Supporting Information file of the original manuscript, the Figure on page 3, "A typical atomic force microscopy (AFM) image evidencing the nanorod morphology", was missing. The Supporting Information file has been revised to include this Figure.

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