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 x 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 VO2+ 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.
Ordered assembly of non-planar vanadyl-tetraphenylporphyrins on ultra-thin iron oxide / G. Albani, L. Schio, F. Goto, A. Calloni, A. Orbelli Biroli, A. Bossi, F. Melone, S. Achilli, G. Fratesi, C. Zucchetti, L. Floreano, G. Bussetti. - In: PHYSICAL CHEMISTRY CHEMICAL PHYSICS. - ISSN 1463-9076. - 24:28(2022 Jul 21), pp. 17077-17087. [10.1039/d1cp05914a]
Ordered assembly of non-planar vanadyl-tetraphenylporphyrins on ultra-thin iron oxide
S. Achilli;G. Fratesi;
2022
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 x 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 VO2+ 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.File | Dimensione | Formato | |
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