Experimental Demonstration of a Spectral Fingerprint for the Saddle and Inverted Conformations of Porphyrins on Copper
(2025) In Journal of Physical Chemistry Letters 16(20). p.5012-5017- Abstract
Combined density functional theory (DFT) and X-ray standing wave (XSW) studies have previously provided evidence for the preferential adoption of an inverted conformation of 2H-TPP on Cu(111) in contrast to the saddle conformation usually favored by porphyrin molecules adsorbed on metals. We experimentally demonstrate, via X-ray photoelectron spectroscopy (XPS) analysis, that the binding energies of the aminic and iminic nitrogen species provide a spectral fingerprint for both inverted and saddle conformations, as predicted by DFT studies. Our complementary scanning tunneling microscopy (STM) characterization also reveals conversion from the saddle to inverted conformation at an elevated temperature for an analogous porphyrin species... (More)
Combined density functional theory (DFT) and X-ray standing wave (XSW) studies have previously provided evidence for the preferential adoption of an inverted conformation of 2H-TPP on Cu(111) in contrast to the saddle conformation usually favored by porphyrin molecules adsorbed on metals. We experimentally demonstrate, via X-ray photoelectron spectroscopy (XPS) analysis, that the binding energies of the aminic and iminic nitrogen species provide a spectral fingerprint for both inverted and saddle conformations, as predicted by DFT studies. Our complementary scanning tunneling microscopy (STM) characterization also reveals conversion from the saddle to inverted conformation at an elevated temperature for an analogous porphyrin species (Br2TPP).
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- author
- Frampton, Eleanor S. LU ; Gray, Ailish ; Clarke, Michael ; Edmondson, Matthew ; Bradford, Jonathan ; Duncan, David A. and Saywell, Alex
- organization
- publishing date
- 2025-05
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Journal of Physical Chemistry Letters
- volume
- 16
- issue
- 20
- pages
- 6 pages
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- pmid:40355097
- scopus:105004799659
- ISSN
- 1948-7185
- DOI
- 10.1021/acs.jpclett.5c00498
- language
- English
- LU publication?
- yes
- id
- 756ab528-935c-446a-a55f-bd3724b23a78
- date added to LUP
- 2025-08-04 12:04:18
- date last changed
- 2025-08-05 03:00:04
@article{756ab528-935c-446a-a55f-bd3724b23a78, abstract = {{<p>Combined density functional theory (DFT) and X-ray standing wave (XSW) studies have previously provided evidence for the preferential adoption of an inverted conformation of 2H-TPP on Cu(111) in contrast to the saddle conformation usually favored by porphyrin molecules adsorbed on metals. We experimentally demonstrate, via X-ray photoelectron spectroscopy (XPS) analysis, that the binding energies of the aminic and iminic nitrogen species provide a spectral fingerprint for both inverted and saddle conformations, as predicted by DFT studies. Our complementary scanning tunneling microscopy (STM) characterization also reveals conversion from the saddle to inverted conformation at an elevated temperature for an analogous porphyrin species (Br<sub>2</sub>TPP).</p>}}, author = {{Frampton, Eleanor S. and Gray, Ailish and Clarke, Michael and Edmondson, Matthew and Bradford, Jonathan and Duncan, David A. and Saywell, Alex}}, issn = {{1948-7185}}, language = {{eng}}, number = {{20}}, pages = {{5012--5017}}, publisher = {{The American Chemical Society (ACS)}}, series = {{Journal of Physical Chemistry Letters}}, title = {{Experimental Demonstration of a Spectral Fingerprint for the Saddle and Inverted Conformations of Porphyrins on Copper}}, url = {{http://dx.doi.org/10.1021/acs.jpclett.5c00498}}, doi = {{10.1021/acs.jpclett.5c00498}}, volume = {{16}}, year = {{2025}}, }