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Coverage‐ and Temperature‐Dependent Metalation and Dehydrogenation of Tetraphenylporphyrin on Cu(111)
Author(s) -
Röckert Michael,
Franke Matthias,
Tariq Quratulain,
Ditze Stefanie,
Stark Michael,
Uffinger Patrick,
Wechsler Daniel,
Singh Upendra,
Xiao Jie,
Marbach Hubertus,
Steinrück HansPeter,
Lytken Ole
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201402420
Subject(s) - dehydrogenation , metalation , scanning tunneling microscope , chemistry , x ray photoelectron spectroscopy , thermal desorption spectroscopy , desorption , tetraphenylporphyrin , crystallography , photochemistry , porphyrin , stereochemistry , catalysis , materials science , nanotechnology , adsorption , organic chemistry , nuclear magnetic resonance , physics
Using temperature‐programmed desorption, supported by X‐ray photoelectron spectroscopy and scanning tunneling microscopy, a comprehensive overview of the main reactions of 5,10,15,20‐tetraphenyl‐21 H ,23 H ‐porphyrin (2HTPP) on Cu(111) as a function of coverage and temperature is obtained. Three reactions were identified: metalation with Cu substrate atoms, stepwise partial dehydrogenation, and finally complete dehydrogenation. At low coverage the reactions are independent of coverage, but at higher coverage metalation becomes faster and partial dehydrogenation slower. This behavior is explained by a weaker interaction between the iminic nitrogen atoms and the Cu(111) surface in the high‐coverage checkerboard structure, leading to faster metalation, and the stabilizing effect of T‐type interactions in the CuTPP islands formed at high coverage after metalation, leading to slower dehydrogenation. Based on the amount of hydrogen released and the appearance in STM, a structure of the partially dehydrogenated molecule is suggested.