Journal article Open Access

Self-assembly of porphyrin nanostructures at the interface between two immiscible liquids

Molina-Osorio, Andrés F.; Cheung, David; O'Dwyer, Colm; Stewart, Andrew A.; Dossot, Manuel; Herzog, Grégoire; Scanlon, Micheál D.


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{
  "description": "<p>One of the many evolved functions of photosynthetic organisms is to synthesize light harvesting nanostructures from photoactive molecules such as porphyrins. Engineering synthetic analogues with optimized molecular order necessary for the efficient capture and harvest of light energy remains challenging. Here, we address this challenge by reporting the self-assembly of zinc(II) meso-tetrakis(4-carboxyphenyl)porphyrins into films of highly ordered nanostructures. The self-assembly process takes place selectively at the interface between two immiscible liquids (water|organic solvent), with kinetically stable interfacial nanostructures formed only at pH values close to the p<em>K</em>a of the carboxyphenyl groups. Molecular dynamics simulations suggest that the assembly process is driven by an interplay between the hydrophobicity gradient at the interface and hydrogen bonding in the formed nanostructure. <em>Ex situ</em> XRD analysis and <em>in situ</em> UV/vis and steady state fluorescence indicates the formation of chlathrate type nanostructures that retain the emission properties of their monomeric constituents. The self-assembly method presented here avoids the use of acidic conditions, additives such as surfactants and external stimuli, offering an alternative for the realization of light-harvesting antennas in artificial photosynthesis technologies.</p>", 
  "license": "https://creativecommons.org/licenses/by/4.0/legalcode", 
  "creator": [
    {
      "affiliation": "The Bernal Institute and Department of Chemical Sciences, School of Natural Sciences, University of Limerick (UL), Limerick V94 T9PX, Ireland", 
      "@id": "https://orcid.org/0000-0001-8356-6381", 
      "@type": "Person", 
      "name": "Molina-Osorio, Andr\u00e9s F."
    }, 
    {
      "affiliation": "School of Chemistry, National University of Ireland, Galway, University Road, Galway, Ireland", 
      "@id": "https://orcid.org/0000-0002-3994-2295", 
      "@type": "Person", 
      "name": "Cheung, David"
    }, 
    {
      "affiliation": "School of Chemistry, and Tyndall National Institute, University College Cork, Cork, T12 YN60 Ireland", 
      "@id": "https://orcid.org/0000-0001-7429-015X", 
      "@type": "Person", 
      "name": "O'Dwyer, Colm"
    }, 
    {
      "affiliation": "The Bernal Institute and Department of Physics, School of Natural Sciences, University of Limerick (UL), Limerick V94 T9PX, Ireland", 
      "@type": "Person", 
      "name": "Stewart, Andrew A."
    }, 
    {
      "affiliation": "CNRS-Universit\u00e9 de Lorraine, LCPME UMR 7564, 405 Rue de Vandoeuvre, 54600 Villers-l\u00e8s-Nancy, France", 
      "@id": "https://orcid.org/0000-0003-0575-025X", 
      "@type": "Person", 
      "name": "Dossot, Manuel"
    }, 
    {
      "affiliation": "CNRS-Universit\u00e9 de Lorraine, LCPME UMR 7564, 405 Rue de Vandoeuvre, 54600 Villers-l\u00e8s-Nancy, France", 
      "@id": "https://orcid.org/0000-0003-1932-9300", 
      "@type": "Person", 
      "name": "Herzog, Gr\u00e9goire"
    }, 
    {
      "affiliation": "The Bernal Institute and Department of Chemical Sciences, School of Natural Sciences, University of Limerick (UL), Limerick V94 T9PX, Ireland", 
      "@id": "https://orcid.org/0000-0001-7951-7085", 
      "@type": "Person", 
      "name": "Scanlon, Miche\u00e1l D."
    }
  ], 
  "headline": "Self-assembly of porphyrin nanostructures at the interface between two immiscible liquids", 
  "image": "https://zenodo.org/static/img/logos/zenodo-gradient-round.svg", 
  "datePublished": "2020-03-06", 
  "url": "https://zenodo.org/record/4587978", 
  "version": "Published", 
  "keywords": [
    "soft interface", 
    "self-assembly", 
    "porphyrin nanostructures", 
    "molecular antennas", 
    "interface between two immiscible liquids"
  ], 
  "@context": "https://schema.org/", 
  "identifier": "https://doi.org/10.1021/acs.jpcc.0c00437", 
  "@id": "https://doi.org/10.1021/acs.jpcc.0c00437", 
  "@type": "ScholarlyArticle", 
  "name": "Self-assembly of porphyrin nanostructures at the interface between two immiscible liquids"
}
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