Crystal-Phase Transitions and Photocatalysis in Supramolecular Scaffolds

Roman V. Kazantsev, Adam J. Dannenhoffer, Adam S. Weingarten, Brian T. Phelan, Boris Harutyunyan, Taner Aytun, Ashwin Narayanan, Daniel J. Fairfield, Job Boekhoven, Hiroaki Sai, Andrew Senesi, Pascual I. O’Dogherty, Liam C. Palmer, Michael J. Bedzyk, Michael R Wasielewski, Samuel I Stupp

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

The energy landscape of a supramolecular material can include different molecular packing configurations that differ in stability and function. We report here on a thermally driven crystalline order transition in the landscape of supramolecular nanostructures formed by charged chromophore amphiphiles in salt-containing aqueous solutions. An irreversible transition was observed from a metastable to a stable crystal phase within the nanostructures. In the stable crystalline phase, the molecules end up organized in a short scroll morphology at high ionic strengths and as long helical ribbons at lower salt content. This is interpreted as the result of the competition between electrostatic repulsive forces and attractive molecular interactions. Only the stable phase forms charge-transfer excitons upon exposure to visible light as indicated by absorbance and fluorescence features, second-order harmonic generation microscopy, and femtosecond transient absorbance spectroscopy. Interestingly, the supramolecular reconfiguration to the stable crystalline phase nanostructures enhances photosensitization of a proton reduction catalyst for hydrogen production.

Original languageEnglish
Pages (from-to)6120-6127
Number of pages8
JournalJournal of the American Chemical Society
Volume139
Issue number17
DOIs
Publication statusPublished - May 3 2017

Fingerprint

Nanostructures
Photocatalysis
Phase Transition
Scaffolds
Phase transitions
Crystalline materials
Crystals
Salts
Molecular Conformation
Photosensitivity Disorders
Amphiphiles
Molecular interactions
Electrostatic force
Chromophores
Harmonic generation
Hydrogen production
Ionic strength
Static Electricity
Excitons
Osmolar Concentration

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Kazantsev, R. V., Dannenhoffer, A. J., Weingarten, A. S., Phelan, B. T., Harutyunyan, B., Aytun, T., ... Stupp, S. I. (2017). Crystal-Phase Transitions and Photocatalysis in Supramolecular Scaffolds. Journal of the American Chemical Society, 139(17), 6120-6127. https://doi.org/10.1021/jacs.6b13156

Crystal-Phase Transitions and Photocatalysis in Supramolecular Scaffolds. / Kazantsev, Roman V.; Dannenhoffer, Adam J.; Weingarten, Adam S.; Phelan, Brian T.; Harutyunyan, Boris; Aytun, Taner; Narayanan, Ashwin; Fairfield, Daniel J.; Boekhoven, Job; Sai, Hiroaki; Senesi, Andrew; O’Dogherty, Pascual I.; Palmer, Liam C.; Bedzyk, Michael J.; Wasielewski, Michael R; Stupp, Samuel I.

In: Journal of the American Chemical Society, Vol. 139, No. 17, 03.05.2017, p. 6120-6127.

Research output: Contribution to journalArticle

Kazantsev, RV, Dannenhoffer, AJ, Weingarten, AS, Phelan, BT, Harutyunyan, B, Aytun, T, Narayanan, A, Fairfield, DJ, Boekhoven, J, Sai, H, Senesi, A, O’Dogherty, PI, Palmer, LC, Bedzyk, MJ, Wasielewski, MR & Stupp, SI 2017, 'Crystal-Phase Transitions and Photocatalysis in Supramolecular Scaffolds', Journal of the American Chemical Society, vol. 139, no. 17, pp. 6120-6127. https://doi.org/10.1021/jacs.6b13156
Kazantsev RV, Dannenhoffer AJ, Weingarten AS, Phelan BT, Harutyunyan B, Aytun T et al. Crystal-Phase Transitions and Photocatalysis in Supramolecular Scaffolds. Journal of the American Chemical Society. 2017 May 3;139(17):6120-6127. https://doi.org/10.1021/jacs.6b13156
Kazantsev, Roman V. ; Dannenhoffer, Adam J. ; Weingarten, Adam S. ; Phelan, Brian T. ; Harutyunyan, Boris ; Aytun, Taner ; Narayanan, Ashwin ; Fairfield, Daniel J. ; Boekhoven, Job ; Sai, Hiroaki ; Senesi, Andrew ; O’Dogherty, Pascual I. ; Palmer, Liam C. ; Bedzyk, Michael J. ; Wasielewski, Michael R ; Stupp, Samuel I. / Crystal-Phase Transitions and Photocatalysis in Supramolecular Scaffolds. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 17. pp. 6120-6127.
@article{9c298290a4394c83b775124049531ec8,
title = "Crystal-Phase Transitions and Photocatalysis in Supramolecular Scaffolds",
abstract = "The energy landscape of a supramolecular material can include different molecular packing configurations that differ in stability and function. We report here on a thermally driven crystalline order transition in the landscape of supramolecular nanostructures formed by charged chromophore amphiphiles in salt-containing aqueous solutions. An irreversible transition was observed from a metastable to a stable crystal phase within the nanostructures. In the stable crystalline phase, the molecules end up organized in a short scroll morphology at high ionic strengths and as long helical ribbons at lower salt content. This is interpreted as the result of the competition between electrostatic repulsive forces and attractive molecular interactions. Only the stable phase forms charge-transfer excitons upon exposure to visible light as indicated by absorbance and fluorescence features, second-order harmonic generation microscopy, and femtosecond transient absorbance spectroscopy. Interestingly, the supramolecular reconfiguration to the stable crystalline phase nanostructures enhances photosensitization of a proton reduction catalyst for hydrogen production.",
author = "Kazantsev, {Roman V.} and Dannenhoffer, {Adam J.} and Weingarten, {Adam S.} and Phelan, {Brian T.} and Boris Harutyunyan and Taner Aytun and Ashwin Narayanan and Fairfield, {Daniel J.} and Job Boekhoven and Hiroaki Sai and Andrew Senesi and O’Dogherty, {Pascual I.} and Palmer, {Liam C.} and Bedzyk, {Michael J.} and Wasielewski, {Michael R} and Stupp, {Samuel I}",
year = "2017",
month = "5",
day = "3",
doi = "10.1021/jacs.6b13156",
language = "English",
volume = "139",
pages = "6120--6127",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "17",

}

TY - JOUR

T1 - Crystal-Phase Transitions and Photocatalysis in Supramolecular Scaffolds

AU - Kazantsev, Roman V.

AU - Dannenhoffer, Adam J.

AU - Weingarten, Adam S.

AU - Phelan, Brian T.

AU - Harutyunyan, Boris

AU - Aytun, Taner

AU - Narayanan, Ashwin

AU - Fairfield, Daniel J.

AU - Boekhoven, Job

AU - Sai, Hiroaki

AU - Senesi, Andrew

AU - O’Dogherty, Pascual I.

AU - Palmer, Liam C.

AU - Bedzyk, Michael J.

AU - Wasielewski, Michael R

AU - Stupp, Samuel I

PY - 2017/5/3

Y1 - 2017/5/3

N2 - The energy landscape of a supramolecular material can include different molecular packing configurations that differ in stability and function. We report here on a thermally driven crystalline order transition in the landscape of supramolecular nanostructures formed by charged chromophore amphiphiles in salt-containing aqueous solutions. An irreversible transition was observed from a metastable to a stable crystal phase within the nanostructures. In the stable crystalline phase, the molecules end up organized in a short scroll morphology at high ionic strengths and as long helical ribbons at lower salt content. This is interpreted as the result of the competition between electrostatic repulsive forces and attractive molecular interactions. Only the stable phase forms charge-transfer excitons upon exposure to visible light as indicated by absorbance and fluorescence features, second-order harmonic generation microscopy, and femtosecond transient absorbance spectroscopy. Interestingly, the supramolecular reconfiguration to the stable crystalline phase nanostructures enhances photosensitization of a proton reduction catalyst for hydrogen production.

AB - The energy landscape of a supramolecular material can include different molecular packing configurations that differ in stability and function. We report here on a thermally driven crystalline order transition in the landscape of supramolecular nanostructures formed by charged chromophore amphiphiles in salt-containing aqueous solutions. An irreversible transition was observed from a metastable to a stable crystal phase within the nanostructures. In the stable crystalline phase, the molecules end up organized in a short scroll morphology at high ionic strengths and as long helical ribbons at lower salt content. This is interpreted as the result of the competition between electrostatic repulsive forces and attractive molecular interactions. Only the stable phase forms charge-transfer excitons upon exposure to visible light as indicated by absorbance and fluorescence features, second-order harmonic generation microscopy, and femtosecond transient absorbance spectroscopy. Interestingly, the supramolecular reconfiguration to the stable crystalline phase nanostructures enhances photosensitization of a proton reduction catalyst for hydrogen production.

UR - http://www.scopus.com/inward/record.url?scp=85018254896&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85018254896&partnerID=8YFLogxK

U2 - 10.1021/jacs.6b13156

DO - 10.1021/jacs.6b13156

M3 - Article

C2 - 28436654

AN - SCOPUS:85018254896

VL - 139

SP - 6120

EP - 6127

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 17

ER -