Functionalized Porphyrins on an Atomically Defined Oxide Surface: Anchoring and Coverage-Dependent Reorientation of MCTPP on Co3O4(111)

The Journal of Physical Chemistry Letters
Kristin WernerJörg Libuda

Abstract

We have studied the adsorption of tetraphenylporphyrin (2HTPP) and its carboxylated counterpart mono-para-carboxyphenyltriphenylporphyrin (MCTPP) on an atomically defined Co3O4(111) film under ultrahigh vacuum (UHV) conditions. Using time-resolved infrared reflection absorption spectroscopy (TR-IRAS), we show that 2HTPP adsorbs molecularly in a flat-lying orientation, whereas MCTPP binds to the surface via formation of a chelating bidentate carboxylate upon deposition at 400 K. Combining TR-IRAS and density-functional theory (DFT), we determine the molecular tilting angle as a function of coverage. We show that the MCTPP adsorption geometry changes from a nearly flat-lying orientation (tilting angle <30°) at low coverage to a nearly perfectly upright-standing orientation (tilting angle of approximately 80°) in the full monolayer.

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Citations

Sep 13, 2017·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Tao XuJoerg Libuda
May 24, 2018·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Fabian KollhoffJörg Libuda
Sep 20, 2018·Physical Chemistry Chemical Physics : PCCP·Fabian KollhoffJörg Libuda
Mar 12, 2019·Analytical Sciences : the International Journal of the Japan Society for Analytical Chemistry·Yan YangHaowen Huang
Aug 14, 2019·Chemistry : a European Journal·Daniel WechslerOle Lytken
Jun 5, 2019·Nature Communications·Christian SchuschkeJörg Libuda
Aug 22, 2020·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Elmar KataevOle Lytken
Oct 24, 2020·Beilstein Journal of Nanotechnology·Feifei XiangM Alexander Schneider
Jun 3, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Daniel WechslerOle Lytken
Apr 14, 2017·Langmuir : the ACS Journal of Surfaces and Colloids·Susanne MohrJörg Libuda
Mar 30, 2018·The Journal of Physical Chemistry Letters·Christian SchuschkeJörg Libuda

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