Molecular Packing of Amphiphilic Nanosheets Resolved by X-ray Scattering

Boris Harutyunyan, Adam Dannenhoffer, Sumit Kewalramani, Taner Aytun, Daniel J. Fairfield, Samuel I Stupp, Michael J. Bedzyk

Research output: Contribution to journalArticle

4 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)1047-1054
Number of pages8
JournalJournal of Physical Chemistry C
Volume121
Issue number2
DOIs
Publication statusPublished - Jan 19 2017

Fingerprint

Nanosheets
X ray scattering
Diffraction patterns
assemblies
diffraction patterns
Perylene
scattering
x rays
rings
Chromophores
chromophores
Conversion efficiency
line shape
Crystal structure
Sodium
sodium
Scattering
formalism
crystal structure

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Surfaces, Coatings and Films
  • Physical and Theoretical Chemistry

Cite this

Harutyunyan, B., Dannenhoffer, A., Kewalramani, S., Aytun, T., Fairfield, D. J., Stupp, S. I., & Bedzyk, M. J. (2017). Molecular Packing of Amphiphilic Nanosheets Resolved by X-ray Scattering. Journal of Physical Chemistry C, 121(2), 1047-1054. https://doi.org/10.1021/acs.jpcc.6b11391

Molecular Packing of Amphiphilic Nanosheets Resolved by X-ray Scattering. / Harutyunyan, Boris; Dannenhoffer, Adam; Kewalramani, Sumit; Aytun, Taner; Fairfield, Daniel J.; Stupp, Samuel I; Bedzyk, Michael J.

In: Journal of Physical Chemistry C, Vol. 121, No. 2, 19.01.2017, p. 1047-1054.

Research output: Contribution to journalArticle

Harutyunyan, B, Dannenhoffer, A, Kewalramani, S, Aytun, T, Fairfield, DJ, Stupp, SI & Bedzyk, MJ 2017, 'Molecular Packing of Amphiphilic Nanosheets Resolved by X-ray Scattering', Journal of Physical Chemistry C, vol. 121, no. 2, pp. 1047-1054. https://doi.org/10.1021/acs.jpcc.6b11391
Harutyunyan B, Dannenhoffer A, Kewalramani S, Aytun T, Fairfield DJ, Stupp SI et al. Molecular Packing of Amphiphilic Nanosheets Resolved by X-ray Scattering. Journal of Physical Chemistry C. 2017 Jan 19;121(2):1047-1054. https://doi.org/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. In: Journal of Physical Chemistry C. 2017 ; Vol. 121, No. 2. pp. 1047-1054.
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