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

Authors :
Manuel Dossot
David L. Cheung
Andrew Stewart
Colm O'Dwyer
Grégoire Herzog
Andrés F. Molina-Osorio
Micheál D. Scanlon
Bernal Institute [Limerick, Ireland]
University of Limerick (UL)
School of Chemistry, National University of Ireland Galway
National University of Ireland [Galway] (NUI Galway)
University College Cork (UCC)
Advanced Materials and BioEngineering Research - AMBER (IRELAND)
Laboratoire de Chimie Physique et Microbiologie pour les Matériaux et l'Environnement (LCPME)
Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)
European Research Council Starting Grant (agreement no. 716792)
Science Foundation Ireland (SFI) (grant number 13/SIRG/2137)
Science Foundation Ireland (SFI) under Grant Numbers 13/TIDA/E2761, 14/IA/2581 and 15/TIDA/2893
ANR-15-IDEX-0004,LUE,Isite LUE(2015)
Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)
ERC
SFI
IRC
Irish Centre for High-End Computing
French Programme Investissement d’Avenir
Source :
The Journal of Physical Chemistry C, Journal of Physical Chemistry C, Journal of Physical Chemistry C, American Chemical Society, 2020, ⟨10.1021/acs.jpcc.0c00437⟩
Publication Year :
2020
Publisher :
American Chemical Society, 2020.

Abstract

peer-reviewed The full text of this article will not be available in ULIR until the embargo expires on the 06/03/2021 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 pKa 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. Ex situ XRD analysis and in situ 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.

Details

Language :
English
ISSN :
19327447 and 19327455
Database :
OpenAIRE
Journal :
The Journal of Physical Chemistry C, Journal of Physical Chemistry C, Journal of Physical Chemistry C, American Chemical Society, 2020, ⟨10.1021/acs.jpcc.0c00437⟩
Accession number :
edsair.doi.dedup.....541023eac179d496aca6b635b470a210
Full Text :
https://doi.org/10.1021/acs.jpcc.0c00437⟩