Ordered assembly of non-planar vanadyl-tetraphenylporphyrins on ultra-thin iron oxide. Issue 28 (6th July 2022)

• Record Type: Journal Article
• Authors: Albani, Guglielmo; Schio, Luca; Goto, Francesco; Calloni, Alberto; Orbelli Biroli, Alessio; Bossi, Alberto; Melone, Francesco; Achilli, Simona; Fratesi, Guido; Zucchetti, Carlo; Floreano, Luca; Bussetti, Gianlorenzo
• Is Part Of: Physical chemistry chemical physics. Volume 24:Issue 28(2022)
• Page Start: 17077
• Page End: 17087
• Publication Date: 2022-07-06
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d1cp05914a
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Thanks to the ultrathin oxide layer, an ordered arrangement of flat-lying porphyrins with a protruding core is obtained on Fe(001). Abstract : Stabilizing ordered assemblies of molecules represents the first step towards the construction of molecular devices featuring hybrid (organic–inorganic) interfaces where molecules can be easily functionalized in view of specific applications. Molecular layers of planar metal-tetraphenylporphyrins (MTPP) grown on an ultrathin iron oxide [namely Fe(001)– p (1 × 1)O] show indeed a high degree of structural order. The generality of such a picture is tested by exploiting non-planar porphyrins, such as vanadyl-TPP (VOTPP). These molecules feature a VO 2+ ion in their center, with the O atom protruding out of the plane of the porphyrin ring. In this work, by employing diffraction, photoemission and X-ray absorption, we prove that non-planar VOTPP can nevertheless form a square and ordered superstructure, where porphyrin molecules lie flat with respect to the underlying substrate. Ab initio density functional theory simulations are used to elucidate the VO bond orientation with respect to the iron substrate.