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A switchable self-assembling and disassembling chiral system based on a porphyrin-substituted phenylalanine–phenylalanine motif

A switchable self-assembling and disassembling chiral system based on a porphyrin-substituted phenylalanine–phenylalanine motif
A switchable self-assembling and disassembling chiral system based on a porphyrin-substituted phenylalanine–phenylalanine motif
Artificial light-harvesting systems have until now not been able to self-assemble into structures with a large photon capture cross-section that upon a stimulus reversibly can switch into an inactive state. Here we describe a simple and robust FLFL-dipeptide construct to which a meso-tetraphenylporphyrin has been appended and which self-assembles to fibrils, platelets or nanospheres depending on the solvent composition. The fibrils, functioning as quenched antennas, give intense excitonic couplets in the electronic circular dichroism spectra which are mirror imaged if the unnatural FDFD-analogue is used. By slightly increasing the solvent polarity, these light-harvesting fibres disassemble to spherical structures with silent electronic circular dichroism spectra but which fluoresce. Upon further dilution with the nonpolar solvent, the intense Cotton effects are recovered, thus proving a reversible switching. A single crystal X-ray structure shows a head-to-head arrangement of porphyrins that explains both their excitonic coupling and quenched fluorescence.
1-11
Charalambidis, Georgios
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Georgilis, Evangelos
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Panda, Manas K.
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Anson, Christopher E.
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Powell, Annie K.
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Doyle, Stephen
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Moss, David
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Jochum, Tobias
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Horton, Peter
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Coles, Simon
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Linares, Mathieu
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Beljonne, David
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Naubron, Jean-Valère
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Conradt, Jonas
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Kalt, Heinz
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Mitraki, Anna
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Coutsolelos, Athanassios G.
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Balaban, Teodor Silviu
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Charalambidis, Georgios
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Georgilis, Evangelos
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Panda, Manas K.
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Anson, Christopher E.
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Powell, Annie K.
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Doyle, Stephen
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Moss, David
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Jochum, Tobias
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Horton, Peter
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Coles, Simon
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Linares, Mathieu
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Beljonne, David
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Naubron, Jean-Valère
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Conradt, Jonas
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Kalt, Heinz
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Mitraki, Anna
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Coutsolelos, Athanassios G.
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Balaban, Teodor Silviu
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Charalambidis, Georgios, Georgilis, Evangelos, Panda, Manas K., Anson, Christopher E., Powell, Annie K., Doyle, Stephen, Moss, David, Jochum, Tobias, Horton, Peter, Coles, Simon, Linares, Mathieu, Beljonne, David, Naubron, Jean-Valère, Conradt, Jonas, Kalt, Heinz, Mitraki, Anna, Coutsolelos, Athanassios G. and Balaban, Teodor Silviu (2016) A switchable self-assembling and disassembling chiral system based on a porphyrin-substituted phenylalanine–phenylalanine motif. Nature Communications, 7 (12657), 1-11. (doi:10.1038/ncomms12657).

Record type: Article

Abstract

Artificial light-harvesting systems have until now not been able to self-assemble into structures with a large photon capture cross-section that upon a stimulus reversibly can switch into an inactive state. Here we describe a simple and robust FLFL-dipeptide construct to which a meso-tetraphenylporphyrin has been appended and which self-assembles to fibrils, platelets or nanospheres depending on the solvent composition. The fibrils, functioning as quenched antennas, give intense excitonic couplets in the electronic circular dichroism spectra which are mirror imaged if the unnatural FDFD-analogue is used. By slightly increasing the solvent polarity, these light-harvesting fibres disassemble to spherical structures with silent electronic circular dichroism spectra but which fluoresce. Upon further dilution with the nonpolar solvent, the intense Cotton effects are recovered, thus proving a reversible switching. A single crystal X-ray structure shows a head-to-head arrangement of porphyrins that explains both their excitonic coupling and quenched fluorescence.

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More information

Accepted/In Press date: 18 July 2016
e-pub ahead of print date: 1 September 2016
Published date: 1 September 2016
Organisations: Characterisation and Analytics, Organic Chemistry: SCF

Identifiers

Local EPrints ID: 402138
URI: https://eprints.soton.ac.uk/id/eprint/402138
PURE UUID: 9ee14d5f-f07e-4602-97af-b1658a4dea84
ORCID for Peter Horton: ORCID iD orcid.org/0000-0001-8886-2016
ORCID for Simon Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 01 Nov 2016 17:08
Last modified: 20 Jul 2019 01:10

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