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.

doi:10.1021/acs.jpcc.6b11391

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

Journal Article · Thu Dec 29 00:00:00 EST 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b11391· OSTI ID:1821168

Harutyunyan, Boris ^[1]; Dannenhoffer, Adam ^[1]; Kewalramani, Sumit ^[1]; Aytun, Taner ^[1]; Fairfield, Daniel J. ^[1];

^[1];

^[1]

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

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.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001059; FG02-08ER46539; AC02-06CH11357

OSTI ID:: 1821168

Alternate ID(s):: OSTI ID: 1846947

Journal Information:: Journal of Physical Chemistry. C, Vol. 121, Issue 2; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 17 works

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