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Title: Molecular Packing of Amphiphilic Nanosheets Resolved by X-ray Scattering

Abstract

Molecular packing in light harvesting 2D assemblies of photocatalytic materials is a critical factor for solar-to-fuel conversion efficiency. However, structure–function correlations have yet to be fully established. This is partly due to the difficulties in extracting the molecular arrangements from the complex 3D powder averaged diffraction patterns of 2D lattices, obtained via in situ wide-angle X-ray scattering. Here, we develop a scattering theory formalism and couple it with a simple geometrical model for the molecular shape of chromophore 9-methoxy-N-(sodium hexanoate)perylene-3,4-dicarboximide (MeO-PMI) used in our study. This generally applicable method fully reproduces the measured diffraction pattern including the asymmetric line shapes for the Bragg reflections and yields the molecular packing arrangement within a 2D crystal structure with a remarkable degree of detail. We find an approximate edge-centered herringbone structure for the PMI fused aromatic rings and ordering of the carboxypentyl chains above and below the nanosheets. Such a packing arrangement differs from the more symmetric face-to-face orientation of the unsubstituted PMI rings. This structural difference is correlated to our measurement of the reduced catalytic performance of MeO-PMI nanosheets as compared to the mesoscopically similar unsubstituted PMI assemblies.

Authors:
; ; ; ; ; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1343133
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 2; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
ENGLISH
Subject:
36 MATERIALS SCIENCE

Citation Formats

Harutyunyan, Boris, Dannenhoffer, Adam, Kewalramani, Sumit, Aytun, Taner, Fairfield, Daniel J., Stupp, Samuel I., and Bedzyk, Michael J. Molecular Packing of Amphiphilic Nanosheets Resolved by X-ray Scattering. United States: N. p., 2016. Web. doi:10.1021/acs.jpcc.6b11391.
Harutyunyan, Boris, Dannenhoffer, Adam, Kewalramani, Sumit, Aytun, Taner, Fairfield, Daniel J., Stupp, Samuel I., & Bedzyk, Michael J. Molecular Packing of Amphiphilic Nanosheets Resolved by X-ray Scattering. United States. https://doi.org/10.1021/acs.jpcc.6b11391
Harutyunyan, Boris, Dannenhoffer, Adam, Kewalramani, Sumit, Aytun, Taner, Fairfield, Daniel J., Stupp, Samuel I., and Bedzyk, Michael J. 2016. "Molecular Packing of Amphiphilic Nanosheets Resolved by X-ray Scattering". United States. https://doi.org/10.1021/acs.jpcc.6b11391.
@article{osti_1343133,
title = {Molecular Packing of Amphiphilic Nanosheets Resolved by X-ray Scattering},
author = {Harutyunyan, Boris and Dannenhoffer, Adam and Kewalramani, Sumit and Aytun, Taner and Fairfield, Daniel J. and Stupp, Samuel I. and Bedzyk, Michael J.},
abstractNote = {Molecular packing in light harvesting 2D assemblies of photocatalytic materials is a critical factor for solar-to-fuel conversion efficiency. However, structure–function correlations have yet to be fully established. This is partly due to the difficulties in extracting the molecular arrangements from the complex 3D powder averaged diffraction patterns of 2D lattices, obtained via in situ wide-angle X-ray scattering. Here, we develop a scattering theory formalism and couple it with a simple geometrical model for the molecular shape of chromophore 9-methoxy-N-(sodium hexanoate)perylene-3,4-dicarboximide (MeO-PMI) used in our study. This generally applicable method fully reproduces the measured diffraction pattern including the asymmetric line shapes for the Bragg reflections and yields the molecular packing arrangement within a 2D crystal structure with a remarkable degree of detail. We find an approximate edge-centered herringbone structure for the PMI fused aromatic rings and ordering of the carboxypentyl chains above and below the nanosheets. Such a packing arrangement differs from the more symmetric face-to-face orientation of the unsubstituted PMI rings. This structural difference is correlated to our measurement of the reduced catalytic performance of MeO-PMI nanosheets as compared to the mesoscopically similar unsubstituted PMI assemblies.},
doi = {10.1021/acs.jpcc.6b11391},
url = {https://www.osti.gov/biblio/1343133}, journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 2,
volume = 121,
place = {United States},
year = {Thu Dec 29 00:00:00 EST 2016},
month = {Thu Dec 29 00:00:00 EST 2016}
}

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