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Title: Molecular Control of Internal Crystallization and Photocatalytic Function in Supramolecular Nanostructures

Abstract

Supramolecular light-absorbing nanostructures are useful building blocks for the design of next-generation artificial photosynthetic systems. Development of such systems requires a detailed understanding of how molecular packing influences the material's optoelectronic properties. We describe a series of crystalline supramolecular nanostructures in which the substituents on their monomeric units strongly affect morphology, ordering kinetics, and exciton behavior. By designing constitutionally isomeric perylene monoimide (PMI) amphiphiles, we studied the effect of side chain sterics on nanostructure crystallization. Molecules with short amine-linked alkyl tails rapidly crystallize upon dissolution in water, whereas bulkier tails require the addition of salt to screen electrostatic repulsion and annealing to drive crystallization. A PMI monomer bearing a 3-pentylamine tail was found to possess a unique structure that results in strongly red-shifted absorbance, indicative of charge-transfer exciton formation. This particular supramolecular structure was found to have an enhanced ability to photosensitize a thiomolybdate catalyst ((NH4)2Mo3S13) to generate hydrogen gas.

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES); Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1562969
Alternate Identifier(s):
OSTI ID: 1822188; OSTI ID: 1846785
Grant/Contract Number:  
SC0001059; AC02-06CH11357
Resource Type:
Published Article
Journal Name:
Chem
Additional Journal Information:
Journal Name: Chem Journal Volume: 4 Journal Issue: 7; Journal ID: ISSN 2451-9294
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 99 GENERAL AND MISCELLANEOUS; rylene; supramolecular chemistry; photocatalysis; charge-transfer; exciton; crystallization

Citation Formats

Kazantsev, Roman V., Dannenhoffer, Adam J., Aytun, Taner, Harutyunyan, Boris, Fairfield, Daniel J., Bedzyk, Michael J., and Stupp, Samuel I. Molecular Control of Internal Crystallization and Photocatalytic Function in Supramolecular Nanostructures. United States: N. p., 2018. Web. doi:10.1016/j.chempr.2018.04.002.
Kazantsev, Roman V., Dannenhoffer, Adam J., Aytun, Taner, Harutyunyan, Boris, Fairfield, Daniel J., Bedzyk, Michael J., & Stupp, Samuel I. Molecular Control of Internal Crystallization and Photocatalytic Function in Supramolecular Nanostructures. United States. https://doi.org/10.1016/j.chempr.2018.04.002
Kazantsev, Roman V., Dannenhoffer, Adam J., Aytun, Taner, Harutyunyan, Boris, Fairfield, Daniel J., Bedzyk, Michael J., and Stupp, Samuel I. Sun . "Molecular Control of Internal Crystallization and Photocatalytic Function in Supramolecular Nanostructures". United States. https://doi.org/10.1016/j.chempr.2018.04.002.
@article{osti_1562969,
title = {Molecular Control of Internal Crystallization and Photocatalytic Function in Supramolecular Nanostructures},
author = {Kazantsev, Roman V. and Dannenhoffer, Adam J. and Aytun, Taner and Harutyunyan, Boris and Fairfield, Daniel J. and Bedzyk, Michael J. and Stupp, Samuel I.},
abstractNote = {Supramolecular light-absorbing nanostructures are useful building blocks for the design of next-generation artificial photosynthetic systems. Development of such systems requires a detailed understanding of how molecular packing influences the material's optoelectronic properties. We describe a series of crystalline supramolecular nanostructures in which the substituents on their monomeric units strongly affect morphology, ordering kinetics, and exciton behavior. By designing constitutionally isomeric perylene monoimide (PMI) amphiphiles, we studied the effect of side chain sterics on nanostructure crystallization. Molecules with short amine-linked alkyl tails rapidly crystallize upon dissolution in water, whereas bulkier tails require the addition of salt to screen electrostatic repulsion and annealing to drive crystallization. A PMI monomer bearing a 3-pentylamine tail was found to possess a unique structure that results in strongly red-shifted absorbance, indicative of charge-transfer exciton formation. This particular supramolecular structure was found to have an enhanced ability to photosensitize a thiomolybdate catalyst ((NH4)2Mo3S13) to generate hydrogen gas.},
doi = {10.1016/j.chempr.2018.04.002},
journal = {Chem},
number = 7,
volume = 4,
place = {United States},
year = {2018},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1016/j.chempr.2018.04.002

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Cited by: 30 works
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