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Stabilization versus competing de-metalation, trans-metalation and (cyclo)-dehydrogenation of Pd porphyrins at a copper surface

Baronio, Stefania ; Bassotti, Mattia ; Armillotta, Francesco ; Frampton, Eleanor LU ; Vinogradov, Nikolay A. LU orcid ; Schio, Luca ; Floreano, Luca ; Verdini, Alberto and Vesselli, Erik (2024) In Nanoscale 16(28). p.13416-13424
Abstract

Metal-porphyrins are studied intensively due their potential applications, deriving from the variety of electronic and chemical properties, tunable by selecting metal centers and functional groups. Metalation, de- and trans-metalation processes are fundamental in this sense to investigate both the synthesis and the stability of these molecular building blocks. More specifically, Pd coordination in tetrapyrroles revealed to be potentially interesting in the fields of cancer therapy, drug delivery and light harvesting. Thus, we focused on the stability of palladium tetraphenyl porphyrins (PdTPPs) on a copper surface by means of combined spectroscopy and microscopy approaches. We find that PdTPPs undergo coverage-dependent trans-metalation... (More)

Metal-porphyrins are studied intensively due their potential applications, deriving from the variety of electronic and chemical properties, tunable by selecting metal centers and functional groups. Metalation, de- and trans-metalation processes are fundamental in this sense to investigate both the synthesis and the stability of these molecular building blocks. More specifically, Pd coordination in tetrapyrroles revealed to be potentially interesting in the fields of cancer therapy, drug delivery and light harvesting. Thus, we focused on the stability of palladium tetraphenyl porphyrins (PdTPPs) on a copper surface by means of combined spectroscopy and microscopy approaches. We find that PdTPPs undergo coverage-dependent trans-metalation accompanied by steric rearrangements already at room temperature, and fully trans-metalate to CuTPPs upon mild annealing. Side reactions such as (cyclo)-dehydrogenation and structural reorganization affect the molecular layer, with Pd-Cu alloying and segregation occurring at higher temperature. Instead, oxygen passivation of the Cu support prevents the metal-involving reactions, thus preserving the layer and increasing the chemical and temperature stability of the Pd porphyrins.

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author
; ; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Nanoscale
volume
16
issue
28
pages
9 pages
publisher
Royal Society of Chemistry
external identifiers
  • pmid:38895999
  • scopus:85196713502
ISSN
2040-3364
DOI
10.1039/d4nr00699b
language
English
LU publication?
yes
id
812b705a-9180-424e-9b3d-2622a7688478
date added to LUP
2024-09-02 10:46:42
date last changed
2025-07-09 05:20:59
@article{812b705a-9180-424e-9b3d-2622a7688478,
  abstract     = {{<p>Metal-porphyrins are studied intensively due their potential applications, deriving from the variety of electronic and chemical properties, tunable by selecting metal centers and functional groups. Metalation, de- and trans-metalation processes are fundamental in this sense to investigate both the synthesis and the stability of these molecular building blocks. More specifically, Pd coordination in tetrapyrroles revealed to be potentially interesting in the fields of cancer therapy, drug delivery and light harvesting. Thus, we focused on the stability of palladium tetraphenyl porphyrins (PdTPPs) on a copper surface by means of combined spectroscopy and microscopy approaches. We find that PdTPPs undergo coverage-dependent trans-metalation accompanied by steric rearrangements already at room temperature, and fully trans-metalate to CuTPPs upon mild annealing. Side reactions such as (cyclo)-dehydrogenation and structural reorganization affect the molecular layer, with Pd-Cu alloying and segregation occurring at higher temperature. Instead, oxygen passivation of the Cu support prevents the metal-involving reactions, thus preserving the layer and increasing the chemical and temperature stability of the Pd porphyrins.</p>}},
  author       = {{Baronio, Stefania and Bassotti, Mattia and Armillotta, Francesco and Frampton, Eleanor and Vinogradov, Nikolay A. and Schio, Luca and Floreano, Luca and Verdini, Alberto and Vesselli, Erik}},
  issn         = {{2040-3364}},
  language     = {{eng}},
  month        = {{06}},
  number       = {{28}},
  pages        = {{13416--13424}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Nanoscale}},
  title        = {{Stabilization versus competing de-metalation, trans-metalation and (cyclo)-dehydrogenation of Pd porphyrins at a copper surface}},
  url          = {{http://dx.doi.org/10.1039/d4nr00699b}},
  doi          = {{10.1039/d4nr00699b}},
  volume       = {{16}},
  year         = {{2024}},
}