Coverage- and Temperature-Dependent Metalation and Dehydrogenation of Tetraphenylporphyrin on Cu(111)
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‐21H,23H‐porphyrin (2HTPP) on Cu(111) as a function of coverage and temperature is obtained. Three reactio...
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Published in | Chemistry : a European journal Vol. 20; no. 29; pp. 8948 - 8953 |
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Main Authors | , , , , , , , , , , , |
Format | Journal Article |
Language | English |
Published |
Weinheim
WILEY-VCH Verlag
14.07.2014
WILEY‐VCH Verlag Wiley Subscription Services, Inc |
Subjects | |
Online Access | Get full text |
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Summary: | 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‐21H,23H‐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.
Small loss: The release of hydrogen during the metalation and dehydrogenation of tetraphenylporphyrin on Cu(111) has been followed with temperature‐programmed desorption, and supported by X‐ray photoelectron spectroscopy and scanning tunneling microscopy. The results provide a detailed overview of the reactions as a function of coverage and temperature and identify the structure of the partially dehydrogenated intermediate. |
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Bibliography: | DFG - No. FOR 1878 istex:323F1369A9C5C27D1EB19B111421958FCF4E84EA Alexander von Humboldt Foundation ark:/67375/WNG-89CKXBGS-C ArticleID:CHEM201402420 ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 0947-6539 1521-3765 |
DOI: | 10.1002/chem.201402420 |