Chromophore Dipole Directs Morphology and Photocatalytic Hydrogen Generation

Weingarten, Adam S.; Dannenhoffer, Adam J.; Kazantsev, Roman V.; Sai, Hiroaki; Huang, Dongxu; Stupp, Samuel I.

doi:10.1021/jacs.7b12641

Chromophore Dipole Directs Morphology and Photocatalytic Hydrogen Generation

Journal Article · Fri Apr 06 00:00:00 EDT 2018 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.7b12641· OSTI ID:1821915

Weingarten, Adam S. ^[1]; Dannenhoffer, Adam J. ^[2]; Kazantsev, Roman V. ^[2]; ^[3]; Huang, Dongxu ^[2]; ^[4]

Northwestern Univ., Evanston, IL (United States); CBES
Northwestern Univ., Evanston, IL (United States)
Northwestern Univ., Chicago, IL (United States)
Northwestern Univ., Evanston, IL (United States); Northwestern Univ., Chicago, IL (United States)

The spontaneous self-assembly of chromophores into light-harvesting antennae provides a potentially low-cost approach to building solar-to-fuel conversion materials. However, designing such supramolecular architectures requires a better understanding of the balance between noncovalent forces among the molecular components. Here, we investigated the aqueous assembly of perylene monoimide chromophore amphiphiles synthesized with different substituents in the 9-position. The molecular dipole strength decreases as the nature of the substituent is altered from electron donating to electron withdrawing. Compounds with stronger molecular dipoles, in which dipolar interactions stabilize assemblies by 10–15 kJ·mol^–1, were found to form crystalline nanoribbons in solution. In contrast, when the molecular dipole moment is small, nanofibers were obtained. Highly blue-shifted absorption maxima were observed in assemblies with large dipoles, indicating strong electronic coupling is present. However, only the moderate dipole compound had the appropriate molecular packing to access charge-transfer excitons leading to enhanced photocatalytic H₂ production.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER); Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES); Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: National Center for Research Resources; National Institutes of Health (NIH); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; SC0001059

OSTI ID:: 1821915

Alternate ID(s):: OSTI ID: 1846786
OSTI ID: 1434718

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 15 Vol. 140; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Internal electric field engineering for steering photogenerated charge separation and enhancing photoactivity Guo, Yan; Shi, Wenxin; Zhu, Yongfa EcoMat, Vol. 1, Issue 1 https://doi.org/10.1002/eom2.12007	journal	December 2019
Impact of charge switching stimuli on supramolecular perylene monoimide assemblies Dannenhoffer, Adam; Sai, Hiroaki; Huang, Dongxu Chemical Science, Vol. 10, Issue 22 https://doi.org/10.1039/c8sc05595e	journal	January 2019
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