Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 7, Issue 3, Pages 555-560Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.5b02784
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Funding
- Deutsche Forschungsgemeinschaft (DFG) within the Research Unit FOR 1878
- Deutsche Forschungsgemeinschaft (DFG) within the DACH Project COMCAT
- Deutsche Forschungsgemeinschaft (DFG) within the Excellence Cluster Engineering of Advanced Materials
- China Scholarship Council (CSC)
- COST Action [CM1104]
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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 degrees) at low coverage to a nearly perfectly upright-standing orientation (tilting angle of approximately 80 degrees) in the full monolayer.
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