Thermally Activated Self-metalation of Carboxy-functionalized Porphyrin Films on MgO Nanocubes

Journal article


Publication Details

Author(s): Kollhoff F, Schneider J, Berger T, Diwald O, Libuda J
Journal: Chemphyschem
Publisher: WILEY-V C H VERLAG GMBH
Publication year: 2018
Volume: 19
Journal issue: 17
Pages range: 2272-2280
ISSN: 1439-4235


Abstract

We investigated the adsorption of different free-base carboxyl-functionalized porphyrins, 5,10,15,20-tetrakis(4-carboxyphenyl)-21,23H-porphyrin (2H-TCPP) and 5(4-carboxyphenyl)-10,15,20-triphenyl-21,23H-porphyrin (2H-MCTPP), on MgO nanocubes combining IR, UV/Vis and photoluminescence emission spectroscopy. The thermal behavior of the films was monitored in-situ during annealing. Both porphyrins bind to the nanocubes via one and two acid groups respectively, yielding monolayer films consisting of tilted molecules. For 2H-TCPP, two acid groups remain free and give rise to a characteristic IR band. Self-assembly in a tilted adsorbate layer suppresses metalation at room temperature, in contrast to non-functionalized 2H-TPP, which adsorbs flat-lying. Upon heating, 2H-MCTPP undergoes full metalation at temperatures below 280 degrees C, whereas 2H-TCPP does not metalate at all. The hindered metalation reaction is attributed to the rigidity of the adsorbate film preventing complexation. Our results show that the properties of porphyrin films on oxides can be tuned in a wide range via the position and arrangement of carboxyl anchoring groups.


FAU Authors / FAU Editors

Kollhoff, Fabian
Lehrstuhl für Physikalische Chemie II
Libuda, Jörg Prof. Dr.
Professur für Physikalische Chemie


Additional Organisation
Exzellenz-Cluster Engineering of Advanced Materials


External institutions with authors

Universität Salzburg (Paris Lodron Universität Salzburg)


Research Fields

D Catalytic Materials
Exzellenz-Cluster Engineering of Advanced Materials


How to cite

APA:
Kollhoff, F., Schneider, J., Berger, T., Diwald, O., & Libuda, J. (2018). Thermally Activated Self-metalation of Carboxy-functionalized Porphyrin Films on MgO Nanocubes. Chemphyschem, 19(17), 2272-2280. https://dx.doi.org/10.1002/cphc.201800152

MLA:
Kollhoff, Fabian, et al. "Thermally Activated Self-metalation of Carboxy-functionalized Porphyrin Films on MgO Nanocubes." Chemphyschem 19.17 (2018): 2272-2280.

BibTeX: 

Last updated on 2019-20-02 at 08:38