University of Limerick
Browse

A soft on/off switch based on the electrochemically reversible H–J interconversion of a floating porphyrin membrane†

Download (890.04 kB)
journal contribution
posted on 2021-07-16, 09:13 authored by Andrés Molina-Osorio, Sho Yamamoto, Iván Robayo-Molina, Alonso Gamero-Quijano, Hirohisa Nagatani, Micheál D. Scanlon
Soft molecular assemblies that respond reversibly to external stimuli are attractive materials as on/off switches, in optoelectronic, memory and sensor technologies. In this Edge Article, we present the reversible structural rearrangement of a soft porphyrin membrane under an electrical potential stimulus in the absence of solid-state architectures. The free-floating porphyrin membrane lies at the interface between immiscible aqueous and organic electrolyte solutions and is formed through interfacial self-assembly of zinc(II) meso-tetrakis(4-carboxyphenyl)porphyrins (ZnPor). A potential difference between the two immiscible electrolyte solutions induces the intercalation of bis(triphenylphosphoranylidene) ammonium cations from the organic electrolyte that exchange with protons in the porphyrin membrane. In situ UV/vis absorbance spectroscopy shows that this ionic intercalation and exchange induces a structural interconversion of the individual porphyrin molecules in the membrane from an H- to a J-type molecular configuration. These structural rearrangements are reversible over 30 potential cycles. In situ polarisation-modulation fluorescence spectroscopy further provides clear evidence of structural interconversion of the porphyrin membrane, as intercalation of the organic electrolyte cations significantly affects the latter's emissive properties. By adjusting the pH of the aqueous phase, additional control of the electrochemically reversible structural interconversion can be achieved, with total suppression at pH 3

Funding

The perceptions of senior management of a semi-state organization on affirmative action

National Research Foundation

Find out more...

Prehistoric Hunting and Herd Management in Kenya

Directorate for Social, Behavioral & Economic Sciences

Find out more...

Using the Cloud to Streamline the Development of Mobile Phone Apps

Innovate UK

Find out more...

History

Publication

Chemical Science; 12,pp.10227-10232

Publisher

The Royal Society of Chemistry

Note

peer-reviewed

Other Funding information

SFI, European Union (EU), IRC, Japan Society for the Promotion of Science

Language

English

Usage metrics

    University of Limerick

    Categories

    No categories selected

    Exports

    RefWorks
    BibTeX
    Ref. manager
    Endnote
    DataCite
    NLM
    DC