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Demetalation of Surface Porphyrins at the Solid-Liquid Interface
Cynthia C Fernández1,2, Matthias Franke3, Hans-Peter Steinrück3
1Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Buenos Aires, Argentina.
Langmuir : the ACS Journal of Surfaces and Colloids
|January 5, 2021
Summary
Surface porphyrins are more stable against metal loss than those in solution. This stability is due to hydrophobic layers hindering proton and ion transport, crucial for designing molecular devices.
Area of Science:
- Surface chemistry
- Materials science
- Molecular electronics
Background:
- Porphyrin metal centers dictate molecular properties.
- Demetalation at the solid-liquid interface is poorly understood.
- Surface-adsorbed porphyrins are key components in molecular devices.
Purpose of the Study:
- Investigate demetalation of surface porphyrins.
- Compare demetalation rates at the solid-liquid interface versus in solution.
- Elucidate factors influencing metal center stability in surface-bound porphyrins.
Main Methods:
- X-ray photoelectron spectroscopy (XPS) was used.
- Studied zinc and cadmium tetraphenylporphyrin (ZnTPP, CdTPP) multilayer films on Au(111).
- Exposed molecular layers to acidic aqueous solutions.
Main Results:
- Surface-adsorbed porphyrins are less prone to demetalation than in solution.
- Hydrophobic porphyrin multilayers impede proton/ion solvation and transport.
- This protective effect is attributed to the interface structure.
Conclusions:
- Porphyrin stability at solid-liquid interfaces is enhanced.
- Interface properties significantly influence molecular behavior.
- Findings are vital for engineering robust porphyrin-based molecular devices.
