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

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.5b10027· OSTI ID:1226681
 [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
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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. Here, we investigated 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. Lastly, 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.

Research Organization:
Northwestern Univ., Evanston, IL (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Inst. of Healh; National Science Foundation (NSF)
Grant/Contract Number:
AC02-06CH11357; SC0001059; 5P41RR007707; 8P41GM103543; DMR-1121262; EEC-0647560; CHE-9871268
OSTI ID:
1226681
Alternate ID(s):
OSTI ID: 1235481; OSTI ID: 1378689; OSTI ID: 1820610
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 137 Journal Issue: 48; ISSN 0002-7863
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 96 works
Citation information provided by
Web of Science

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
77 NANOSCIENCE AND NANOTECHNOLOGY
99 GENERAL AND MISCELLANEOUS
Molecular packing
Nanostructures
Supramolecular structures and assemblies
Solution chemistry
Absorption
Molecular packing
Nanostructures
Supramolecular structures and assemblies
Solution chemistry
Absorption