Interfacial Enrichment and Demetallation of a Zinc Porphyrin in the Ionic Liquid [C4C1Im][PF6]

Ceccatto A, Williams FJ, Maier F, Steinrück HP (2026)

Publication Type: Journal article

Publication year: 2026

Journal

ChemPhysChem Wiley

Book Volume: 27

Article Number: e70318

Journal Issue: 8

DOI: 10.1002/cphc.70318

Abstract

Understanding and controlling the surface composition of metalloporphyrins in ionic liquids (ILs) is crucial for designing photoactive materials. Here, we investigate the interfacial behavior of zinc-didodecylporphyrin molecules (Zn-DDP) dissolved in the hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [C4C1Im][PF6] using angle-resolved X-ray photoelectron spectroscopy (ARXPS). Upon mild heating, Zn-DDP undergoes spontaneous demetallation, evidenced by the appearance of aminic (–NH–) and iminic (=N–) nitrogen XPS signals characteristic of the free-base porphyrins. Partial hydrolysis of [PF6]^- anions produces phosphate species that contribute to the demetallation process. Concentration-dependent measurements reveal extremely high surface enrichment of porphyrins at the IL/vacuum interface, reaching surface saturation already at about 0.50%mol Zn-DDP content in the bulk. The dodecyl chains of porphyrins at the outer surface are oriented toward the vacuum in a buoy-like configuration. Temperature-dependent ARXP spectra reveal that for unsaturated interfaces, surface enrichment increases with increasing temperature. Our findings provide molecular-level insights to guide the design of porphyrin-based photoactive interfaces in ionic liquid systems.

Authors with CRIS profile

Alisson Ceccatto dos Santos Lehrstuhl für Physikalische Chemie II Florian Maier Lehrstuhl für Physikalische Chemie II Hans-Peter Steinrück Lehrstuhl für Physikalische Chemie II

Involved external institutions

Universidad de Buenos Aires (UBA) / University of Buenos Aires

Argentina (AR)

How to cite

APA:

Ceccatto, A., Williams, F.J., Maier, F., & Steinrück, H.-P. (2026). Interfacial Enrichment and Demetallation of a Zinc Porphyrin in the Ionic Liquid [C4C1Im][PF6]. ChemPhysChem, 27(8). https://doi.org/10.1002/cphc.70318

MLA:

Ceccatto, Alisson, et al. "Interfacial Enrichment and Demetallation of a Zinc Porphyrin in the Ionic Liquid [C4C1Im][PF6]." ChemPhysChem 27.8 (2026).

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