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Title: Supramolecular Packing Controls H 2 Photocatalysis in Chromophore Amphiphile Hydrogels

Abstract

© 2015 American Chemical Society.Light harvesting supramolecular assemblies are potentially useful structures as components of solar-to-fuel conversion materials. The development of these functional constructs requires an understanding of optimal packing modes for chromophores. We investigated here assembly in water and the photocatalytic function of perylene monoimide chromophore amphiphiles with different alkyl linker lengths separating their hydrophobic core and the hydrophilic carboxylate headgroup. We found that these chromophore amphiphiles (CAs) self-assemble into charged nanostructures of increasing aspect ratio as the linker length is increased. The addition of salt to screen the charged nanostructures induced the formation of hydrogels and led to internal crystallization within some of the nanostructures. For linker lengths up to seven methylenes, the CAs were found to pack into 2D crystalline unit cells within ribbon-shaped nanostructures, whereas the nine methylene CAs assembled into long nanofibers without crystalline molecular packing. At the same time, the different molecular packing arrangements after charge screening led to different absorbance spectra, despite the identical electronic properties of all PMI amphiphiles. While the crystalline CAs formed electronically coupled H-aggregates, only CAs with intermediate linker lengths showed evidence of high intermolecular orbital overlap. Photocatalytic hydrogen production using a nickel-based catalyst was observed in all hydrogels,more » with the highest turnovers observed for CA gels having intermediate linker lengths. We conclude that the improved photocatalytic performance of the hydrogels formed by supramolecular assemblies of the intermediate linker CA molecules likely arises from improved exciton splitting efficiencies due to their higher orbital overlap.« less

Authors:
 [1];  [1];  [2];  [3];  [3];  [4]
  1. Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States, Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, Illinois 60208, United States
  2. Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States, Simpson Querrey Institute for BioNanotechnology, Northwestern University, Chicago, Illinois 60611, United States
  3. Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208, United States
  4. Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States, Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, Illinois 60208, United States, Simpson Querrey Institute for BioNanotechnology, Northwestern University, Chicago, Illinois 60611, United States, Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208, United States, Department of Medicine, Northwestern University, Chicago, Illinois 60611, United States
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Inst. of Health (NIH) (United States); National Science Foundation (NSF)
OSTI Identifier:
1226681
Alternate Identifier(s):
OSTI ID: 1235481; OSTI ID: 1378689
Grant/Contract Number:  
AC02-06CH11357; SC0001059; 5P41RR007707; 8P41GM103543; DMR-1121262; EEC-0647560; CHE-9871268
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: 137 Journal Issue: 48; 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

Weingarten, Adam S., Kazantsev, Roman V., Palmer, Liam C., Fairfield, Daniel J., Koltonow, Andrew R., and Stupp, Samuel I. Supramolecular Packing Controls H 2 Photocatalysis in Chromophore Amphiphile Hydrogels. United States: N. p., 2015. Web. doi:10.1021/jacs.5b10027.
Weingarten, Adam S., Kazantsev, Roman V., Palmer, Liam C., Fairfield, Daniel J., Koltonow, Andrew R., & Stupp, Samuel I. Supramolecular Packing Controls H 2 Photocatalysis in Chromophore Amphiphile Hydrogels. United States. doi:10.1021/jacs.5b10027.
Weingarten, Adam S., Kazantsev, Roman V., Palmer, Liam C., Fairfield, Daniel J., Koltonow, Andrew R., and Stupp, Samuel I. Sat . "Supramolecular Packing Controls H 2 Photocatalysis in Chromophore Amphiphile Hydrogels". United States. doi:10.1021/jacs.5b10027.
@article{osti_1226681,
title = {Supramolecular Packing Controls H 2 Photocatalysis in Chromophore Amphiphile Hydrogels},
author = {Weingarten, Adam S. and Kazantsev, Roman V. and Palmer, Liam C. and Fairfield, Daniel J. and Koltonow, Andrew R. and Stupp, Samuel I.},
abstractNote = {© 2015 American Chemical Society.Light harvesting supramolecular assemblies are potentially useful structures as components of solar-to-fuel conversion materials. The development of these functional constructs requires an understanding of optimal packing modes for chromophores. We investigated here assembly in water and the photocatalytic function of perylene monoimide chromophore amphiphiles with different alkyl linker lengths separating their hydrophobic core and the hydrophilic carboxylate headgroup. We found that these chromophore amphiphiles (CAs) self-assemble into charged nanostructures of increasing aspect ratio as the linker length is increased. The addition of salt to screen the charged nanostructures induced the formation of hydrogels and led to internal crystallization within some of the nanostructures. For linker lengths up to seven methylenes, the CAs were found to pack into 2D crystalline unit cells within ribbon-shaped nanostructures, whereas the nine methylene CAs assembled into long nanofibers without crystalline molecular packing. At the same time, the different molecular packing arrangements after charge screening led to different absorbance spectra, despite the identical electronic properties of all PMI amphiphiles. While the crystalline CAs formed electronically coupled H-aggregates, only CAs with intermediate linker lengths showed evidence of high intermolecular orbital overlap. Photocatalytic hydrogen production using a nickel-based catalyst was observed in all hydrogels, with the highest turnovers observed for CA gels having intermediate linker lengths. We conclude that the improved photocatalytic performance of the hydrogels formed by supramolecular assemblies of the intermediate linker CA molecules likely arises from improved exciton splitting efficiencies due to their higher orbital overlap.},
doi = {10.1021/jacs.5b10027},
journal = {Journal of the American Chemical Society},
number = 48,
volume = 137,
place = {United States},
year = {2015},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/jacs.5b10027

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Cited by: 17 works
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Works referencing / citing this record:

Reticular synthesis of porous molecular 1D nanotubes and 3D networks
journal, November 2016

  • Slater, A. G.; Little, M. A.; Pulido, A.
  • Nature Chemistry, Vol. 9, Issue 1
  • DOI: 10.1038/nchem.2663

Development of a framework catalyst for photocatalytic hydrogen evolution
journal, January 2018

  • Chinapang, Pondchanok; Okamura, Masaya; Itoh, Takahiro
  • Chemical Communications, Vol. 54, Issue 10
  • DOI: 10.1039/c7cc08013a

A self-assembled perylene diimide nanobelt for efficient visible-light-driven photocatalytic H 2 evolution
journal, January 2019

  • Kong, Kangyi; Zhang, Shicong; Chu, Yanmeng
  • Chemical Communications, Vol. 55, Issue 56
  • DOI: 10.1039/c9cc03465j

Stimuli-triggered reversible switching mechanism between H- and J-type supramolecular assemblies of cationic porphyrins adsorbed on tungsten(VI) oxide surface
journal, August 2018

  • Adachi, Kenta; Ura, Yukimasa; Kanetada, Naoya
  • Journal of Porphyrins and Phthalocyanines, Vol. 22, Issue 08
  • DOI: 10.1142/s1088424618500372

Reticular synthesis of porous molecular 1D nanotubes and 3D networks
journal, November 2016

  • Slater, A. G.; Little, M. A.; Pulido, A.
  • Nature Chemistry, Vol. 9, Issue 1
  • DOI: 10.1038/nchem.2663

Development of a framework catalyst for photocatalytic hydrogen evolution
journal, January 2018

  • Chinapang, Pondchanok; Okamura, Masaya; Itoh, Takahiro
  • Chemical Communications, Vol. 54, Issue 10
  • DOI: 10.1039/c7cc08013a

A self-assembled perylene diimide nanobelt for efficient visible-light-driven photocatalytic H 2 evolution
journal, January 2019

  • Kong, Kangyi; Zhang, Shicong; Chu, Yanmeng
  • Chemical Communications, Vol. 55, Issue 56
  • DOI: 10.1039/c9cc03465j

Stimuli-triggered reversible switching mechanism between H- and J-type supramolecular assemblies of cationic porphyrins adsorbed on tungsten(VI) oxide surface
journal, August 2018

  • Adachi, Kenta; Ura, Yukimasa; Kanetada, Naoya
  • Journal of Porphyrins and Phthalocyanines, Vol. 22, Issue 08
  • DOI: 10.1142/s1088424618500372