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Title: Crystal-Phase Transitions and Photocatalysis in Supramolecular Scaffolds

Abstract

The energy landscape of a supramolecular material can include different molecular packing configurations that differ in stability and function. Here, we report here on a thermally driven crystalline order transition in the landscape of supramolecular nanostructures formed by charged chromophore amphiphiles in salt-containing aqueous solutions. Furthermore, we observed an irreversible transition from a metastable to a stable crystal phase within the nanostructures. In the stable crystalline phase, the molecules end up organized in a short scroll morphology at high ionic strengths and as long helical ribbons at lower salt content. We interpret this as the result of the competition between electrostatic repulsive forces and attractive molecular interactions. Only the stable phase forms charge-transfer excitons upon exposure to visible light as indicated by absorbance and fluorescence features, second-order harmonic generation microscopy, and femtosecond transient absorbance spectroscopy. Interestingly, the supramolecular reconfiguration to the stable crystalline phase nanostructures enhances photosensitization of a proton reduction catalyst for hydrogen production.

Authors:
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  1. X-ray Science Division, Argonne National Laboratory, Argonne, Illinois 60439, United States
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1352707
Alternate Identifier(s):
OSTI ID: 1361505
Grant/Contract Number:  
SC0001059; FG02-00ER45810; AC02-06CH11357; SC0000989
Resource Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society Journal Volume: 139 Journal Issue: 17; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Kazantsev, Roman V., Dannenhoffer, Adam J., Weingarten, Adam S., Phelan, Brian T., Harutyunyan, Boris, Aytun, Taner, Narayanan, Ashwin, Fairfield, Daniel J., Boekhoven, Job, Sai, Hiroaki, Senesi, Andrew, O’Dogherty, Pascual I., Palmer, Liam C., Bedzyk, Michael J., Wasielewski, Michael R., and Stupp, Samuel I. Crystal-Phase Transitions and Photocatalysis in Supramolecular Scaffolds. United States: N. p., 2017. Web. doi:10.1021/jacs.6b13156.
Kazantsev, Roman V., Dannenhoffer, Adam J., Weingarten, Adam S., Phelan, Brian T., Harutyunyan, Boris, Aytun, Taner, Narayanan, Ashwin, Fairfield, Daniel J., Boekhoven, Job, Sai, Hiroaki, Senesi, Andrew, O’Dogherty, Pascual I., Palmer, Liam C., Bedzyk, Michael J., Wasielewski, Michael R., & Stupp, Samuel I. Crystal-Phase Transitions and Photocatalysis in Supramolecular Scaffolds. United States. doi:10.1021/jacs.6b13156.
Kazantsev, Roman V., Dannenhoffer, Adam J., Weingarten, Adam S., Phelan, Brian T., Harutyunyan, Boris, Aytun, Taner, Narayanan, Ashwin, Fairfield, Daniel J., Boekhoven, Job, Sai, Hiroaki, Senesi, Andrew, O’Dogherty, Pascual I., Palmer, Liam C., Bedzyk, Michael J., Wasielewski, Michael R., and Stupp, Samuel I. Mon . "Crystal-Phase Transitions and Photocatalysis in Supramolecular Scaffolds". United States. doi:10.1021/jacs.6b13156.
@article{osti_1352707,
title = {Crystal-Phase Transitions and Photocatalysis in Supramolecular Scaffolds},
author = {Kazantsev, Roman V. and Dannenhoffer, Adam J. and Weingarten, Adam S. and Phelan, Brian T. and Harutyunyan, Boris and Aytun, Taner and Narayanan, Ashwin and Fairfield, Daniel J. and Boekhoven, Job and Sai, Hiroaki and Senesi, Andrew and O’Dogherty, Pascual I. and Palmer, Liam C. and Bedzyk, Michael J. and Wasielewski, Michael R. and Stupp, Samuel I.},
abstractNote = {The energy landscape of a supramolecular material can include different molecular packing configurations that differ in stability and function. Here, we report here on a thermally driven crystalline order transition in the landscape of supramolecular nanostructures formed by charged chromophore amphiphiles in salt-containing aqueous solutions. Furthermore, we observed an irreversible transition from a metastable to a stable crystal phase within the nanostructures. In the stable crystalline phase, the molecules end up organized in a short scroll morphology at high ionic strengths and as long helical ribbons at lower salt content. We interpret this as the result of the competition between electrostatic repulsive forces and attractive molecular interactions. Only the stable phase forms charge-transfer excitons upon exposure to visible light as indicated by absorbance and fluorescence features, second-order harmonic generation microscopy, and femtosecond transient absorbance spectroscopy. Interestingly, the supramolecular reconfiguration to the stable crystalline phase nanostructures enhances photosensitization of a proton reduction catalyst for hydrogen production.},
doi = {10.1021/jacs.6b13156},
journal = {Journal of the American Chemical Society},
number = 17,
volume = 139,
place = {United States},
year = {2017},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/jacs.6b13156

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Cited by: 5 works
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Works referencing / citing this record:

Hydrophobicity and CH/π-interaction-driven self-assembly of amphiphilic aromatic hydrocarbons into nanosheets
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