Heteromolecular Bilayers on a Weakly Interacting Substrate: Physisorptive Bonding and Molecular Distortions of Copper-Hexadecafluorophthalocyanine

Heteromolecular bilayers of π-conjugated organic molecules on metals, considered as model systems for more complex thin film heterostructures, are investigated with respect to their structural and electronic properties. By exploring the influence of the organic-metal interaction strength in bilayer systems, we determine the molecular arrangement in the physisorptive regime for copper-hexadecafluorophthalocyanine (F₁₆CuPc) on Au(111) with intermediate layers of 5,7,12,14-pentacenetetrone and perylene-3,4,9,10-tetracarboxylic diimide. Using the X-ray standing wave technique to distinguish the different molecular layers, we show that these two bilayers are ordered following their deposition sequence. Surprisingly, F₁₆CuPc as the second layer within the heterostructures exhibits an inverted intramolecular distortion compared to its monolayer structure.