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:
- 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}
}
Works referenced in this record:
Self-assembling hydrogel scaffolds for photocatalytic hydrogen production
journal, October 2014
- Weingarten, Adam S.; Kazantsev, Roman V.; Palmer, Liam C.
- Nature Chemistry, Vol. 6, Issue 11
Extended-Charge-Transfer Excitons in Crystalline Supramolecular Photocatalytic Scaffolds
journal, September 2016
- Hestand, Nicholas J.; Kazantsev, Roman V.; Weingarten, Adam S.
- Journal of the American Chemical Society, Vol. 138, Issue 36
Supramolecular Packing Controls H 2 Photocatalysis in Chromophore Amphiphile Hydrogels
journal, November 2015
- Weingarten, Adam S.; Kazantsev, Roman V.; Palmer, Liam C.
- Journal of the American Chemical Society, Vol. 137, Issue 48
Energy landscapes and functions of supramolecular systems
journal, January 2016
- Tantakitti, Faifan; Boekhoven, Job; Wang, Xin
- Nature Materials, Vol. 15, Issue 4
Self-Assembly of Supramolecular Light-Harvesting Arrays from Symmetric Perylene-3,4-dicarboximide Trefoils
journal, April 2014
- Lefler, Kelly M.; Kim, Chul Hoon; Wu, Yi-Lin
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 9
Perylene Bisimide Dye Assemblies as Archetype Functional Supramolecular Materials
journal, August 2015
- Würthner, Frank; Saha-Möller, Chantu R.; Fimmel, Benjamin
- Chemical Reviews, Vol. 116, Issue 3
Macroscopically Aligned Ionic Self‐Assembled Perylene‐Surfactant Complexes within a Polymer Matrix
journal, July 2008
- Laiho, Ari; Smarsly, Bernd M.; Faul, Charl F. J.
- Advanced Functional Materials, Vol. 18, Issue 13
Alignment of a Perylene-Based Ionic Self-Assembly Complex in Thermotropic and Lyotropic Liquid-Crystalline Phases
journal, September 2004
- Zakrevskyy, Y.; Faul, C. F. J.; Guan, Y.
- Advanced Functional Materials, Vol. 14, Issue 9
GIXSGUI : a MATLAB toolbox for grazing-incidence X-ray scattering data visualization and reduction, and indexing of buried three-dimensional periodic nanostructured films
journal, April 2015
- Jiang, Zhang
- Journal of Applied Crystallography, Vol. 48, Issue 3
Small Angle X-ray Scattering for Nanoparticle Research
journal, April 2016
- Li, Tao; Senesi, Andrew J.; Lee, Byeongdu
- Chemical Reviews, Vol. 116, Issue 18
The Crystalline Structures of Carboxylic Acid Monolayers Adsorbed on Graphite
journal, March 2006
- Bickerstaffe, A. K.; Cheah, N. P.; Clarke, S. M.
- The Journal of Physical Chemistry B, Vol. 110, Issue 11
The monolayer structure of 1,2-bis(4-pyridyl)ethylene physisorbed on a graphite surface
journal, July 2012
- Brewer, Adam Y.; Friscic, Tomislav; Day, G. M.
- Molecular Physics, Vol. 111, Issue 1
X‐ray diffraction study of the structure of a monolayer methanol film adsorbed on graphite
journal, October 1990
- Morishige, K.; Kawamura, K.; Kose, A.
- The Journal of Chemical Physics, Vol. 93, Issue 7
Monolayers of polar methane derivatives physisorbed on graphite
journal, May 1992
- Knorr, K.
- Physics Reports, Vol. 214, Issue 2
Thin Film Structure of Tetraceno[2,3- b ]thiophene Characterized by Grazing Incidence X-ray Scattering and Near-Edge X-ray Absorption Fine Structure Analysis
journal, March 2008
- Yuan, Quan; Mannsfeld, Stefan C. B.; Tang, Ming L.
- Journal of the American Chemical Society, Vol. 130, Issue 11
Organic Crystals with Near-Infrared Amplified Spontaneous Emissions Based on 2′-Hydroxychalcone Derivatives: Subtle Structure Modification but Great Property Change
journal, June 2015
- Cheng, Xiao; Wang, Kai; Huang, Shuo
- Angewandte Chemie, Vol. 127, Issue 29
High Mobility of Dithiophene-Tetrathiafulvalene Single-Crystal Organic Field Effect Transistors
journal, January 2004
- Mas-Torrent, Marta; Durkut, Murat; Hadley, Peter
- Journal of the American Chemical Society, Vol. 126, Issue 4
Correlation between Crystal Structure and Mobility in Organic Field-Effect Transistors Based on Single Crystals of Tetrathiafulvalene Derivatives
journal, July 2004
- Mas-Torrent, Marta; Hadley, Peter; Bromley, Stefan T.
- Journal of the American Chemical Society, Vol. 126, Issue 27
Elastomeric Transistor Stamps: Reversible Probing of Charge Transport in Organic Crystals
journal, March 2004
- Sundar, Vikram C.; Zaumseil, Jana; Podzorov, Vitaly
- Science, Vol. 303, Issue 5664, p. 1644-1646
Crystallochromy as a solid-state effect: correlation of molecular conformation, crystal packing and colour in perylene-3,4:9,10-bis(dicarboximide) pigments
journal, February 1989
- Klebe, G.; Graser, F.; Hädicke, E.
- Acta Crystallographica Section B Structural Science, Vol. 45, Issue 1
Lineshape calculations for two-dimensional powder samples
journal, February 1989
- Schildberg, H. P.; Lauter, H. J.
- Surface Science, Vol. 208, Issue 3
Analytic Form for the Static Structure Factor for a Finite Two-Dimensional Harmonic Lattice
journal, July 1981
- Dutta, P.; Sinha, S. K.
- Physical Review Letters, Vol. 47, Issue 1
Fused Thiophene Semiconductors: Crystal Structure-Film Microstructure Transistor Performance Correlations
journal, March 2013
- Youn, Jangdae; Kewalramani, Sumit; Emery, Jonathan D.
- Advanced Functional Materials, Vol. 23, Issue 31
On Accelerated Random Search
journal, January 2004
- Appel, M. J.; LaBarre, R.; Radulovic, D.
- SIAM Journal on Optimization, Vol. 14, Issue 3
Understanding Ground- and Excited-State Properties of Perylene Tetracarboxylic Acid Bisimide Crystals by Means of Quantum Chemical Computations
journal, November 2009
- Zhao, Hong-Mei; Pfister, Johannes; Settels, Volker
- Journal of the American Chemical Society, Vol. 131, Issue 43
Synthesis and Self-Organization of Core-Extended Perylene Tetracarboxdiimides with Branched Alkyl Substituents
journal, August 2006
- Nolde, Fabian; Pisula, Wojciech; Müller, Sibylle
- Chemistry of Materials, Vol. 18, Issue 16
Perylene bisimide dyes as versatile building blocks for functional supramolecular architectures
journal, January 2004
- Würthner, Frank
- Chem. Commun., Issue 14
Crystallochromy of perylene pigments: Interference between Frenkel excitons and charge-transfer states
journal, September 2009
- Gisslén, Linus; Scholz, Reinhard
- Physical Review B, Vol. 80, Issue 11