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Title: Seeded growth of single-crystal two-dimensional covalent organic frameworks

Abstract

Polymerizing monomers into periodic two-dimensional (2D) networks provides structurally precise, layered macromolecular sheets that exhibit desirable mechanical, optoelectrotronic, and molecular transport properties. 2D covalent organic frameworks (COFs) offer broad monomer scope but are generally isolated as powders comprised of aggregated nanometer-scale crystallites. Here we control 2D COF formation using a two-step procedure, in which monomers are added slowly to pre-formed nanoparticle seeds. The resulting 2D COFs are isolated as single-crystalline, micron-sized particles. Transient absorption spectroscopy of the dispersed COF nanoparticles provides two to three orders of magnitude improvement in signal quality relative to polycrystalline powder samples and suggests exciton diffusion over longer length scales than those obtained through previous approaches. These findings will enable a broad exploration of synthetic 2D polymer structures and properties.

Authors:
ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science - Office of Basic Energy Sciences - Scientific User Facilities Division; U.S. Army Research Laboratory - U.S. Army Research Office (ARO)
OSTI Identifier:
1460958
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Science
Additional Journal Information:
Journal Volume: 361; Journal Issue: 6397; Journal ID: ISSN 0036-8075
Publisher:
AAAS
Country of Publication:
United States
Language:
English

Citation Formats

Evans, Austin M., Parent, Lucas R., Flanders, Nathan C., Bisbey, Ryan P., Vitaku, Edon, Kirschner, Matthew S., Schaller, Richard D., Chen, Lin X., Gianneschi, Nathan C., and Dichtel, William R. Seeded growth of single-crystal two-dimensional covalent organic frameworks. United States: N. p., 2018. Web. doi:10.1126/science.aar7883.
Evans, Austin M., Parent, Lucas R., Flanders, Nathan C., Bisbey, Ryan P., Vitaku, Edon, Kirschner, Matthew S., Schaller, Richard D., Chen, Lin X., Gianneschi, Nathan C., & Dichtel, William R. Seeded growth of single-crystal two-dimensional covalent organic frameworks. United States. doi:10.1126/science.aar7883.
Evans, Austin M., Parent, Lucas R., Flanders, Nathan C., Bisbey, Ryan P., Vitaku, Edon, Kirschner, Matthew S., Schaller, Richard D., Chen, Lin X., Gianneschi, Nathan C., and Dichtel, William R. Thu . "Seeded growth of single-crystal two-dimensional covalent organic frameworks". United States. doi:10.1126/science.aar7883.
@article{osti_1460958,
title = {Seeded growth of single-crystal two-dimensional covalent organic frameworks},
author = {Evans, Austin M. and Parent, Lucas R. and Flanders, Nathan C. and Bisbey, Ryan P. and Vitaku, Edon and Kirschner, Matthew S. and Schaller, Richard D. and Chen, Lin X. and Gianneschi, Nathan C. and Dichtel, William R.},
abstractNote = {Polymerizing monomers into periodic two-dimensional (2D) networks provides structurally precise, layered macromolecular sheets that exhibit desirable mechanical, optoelectrotronic, and molecular transport properties. 2D covalent organic frameworks (COFs) offer broad monomer scope but are generally isolated as powders comprised of aggregated nanometer-scale crystallites. Here we control 2D COF formation using a two-step procedure, in which monomers are added slowly to pre-formed nanoparticle seeds. The resulting 2D COFs are isolated as single-crystalline, micron-sized particles. Transient absorption spectroscopy of the dispersed COF nanoparticles provides two to three orders of magnitude improvement in signal quality relative to polycrystalline powder samples and suggests exciton diffusion over longer length scales than those obtained through previous approaches. These findings will enable a broad exploration of synthetic 2D polymer structures and properties.},
doi = {10.1126/science.aar7883},
journal = {Science},
issn = {0036-8075},
number = 6397,
volume = 361,
place = {United States},
year = {2018},
month = {6}
}

Works referenced in this record:

Growth rates and water stability of 2D boronate ester covalent organic frameworks
journal, January 2015

  • Smith, Brian J.; Hwang, Nicky; Chavez, Anton D.
  • Chemical Communications, Vol. 51, Issue 35
  • DOI: 10.1039/C5CC00379B

Oriented 2D Covalent Organic Framework Thin Films on Single-Layer Graphene
journal, April 2011


Phosphoric Acid Loaded Azo (−N═N−) Based Covalent Organic Framework for Proton Conduction
journal, April 2014

  • Chandra, Suman; Kundu, Tanay; Kandambeth, Sharath
  • Journal of the American Chemical Society, Vol. 136, Issue 18
  • DOI: 10.1021/ja502212v

Spectrally Switchable Photodetection with Near-Infrared-Absorbing Covalent Organic Frameworks
journal, August 2017

  • Bessinger, Derya; Ascherl, Laura; Auras, Florian
  • Journal of the American Chemical Society, Vol. 139, Issue 34
  • DOI: 10.1021/jacs.7b06599

The atom, the molecule, and the covalent organic framework
journal, March 2017


Covalent Organic Frameworks as a Platform for Multidimensional Polymerization
journal, May 2017


Synthetic Two-Dimensional Polymers
journal, July 2017


One-Dimensional Singlet Exciton Diffusion in Poly(3-hexylthiophene) Crystalline Domains
journal, January 2014

  • Tamai, Yasunari; Matsuura, Yuu; Ohkita, Hideo
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 2
  • DOI: 10.1021/jz402299a

Lewis acid-catalysed formation of two-dimensional phthalocyanine covalent organic frameworks
journal, June 2010

  • Spitler, Eric L.; Dichtel, William R.
  • Nature Chemistry, Vol. 2, Issue 8, p. 672-677
  • DOI: 10.1038/nchem.695

Gram-scale synthesis of two-dimensional polymer crystals and their structure analysis by X-ray diffraction
journal, July 2014

  • Kory, Max J.; Wörle, Michael; Weber, Thomas
  • Nature Chemistry, Vol. 6, Issue 9
  • DOI: 10.1038/nchem.2007

Mechanistic Studies of Two-Dimensional Covalent Organic Frameworks Rapidly Polymerized from Initially Homogenous Conditions
journal, June 2014

  • Smith, Brian J.; Dichtel, William R.
  • Journal of the American Chemical Society, Vol. 136, Issue 24
  • DOI: 10.1021/ja5037868

Constructing monocrystalline covalent organic networks by polymerization
journal, August 2013

  • Beaudoin, Daniel; Maris, Thierry; Wuest, James D.
  • Nature Chemistry, Vol. 5, Issue 10
  • DOI: 10.1038/nchem.1730

Construction of Covalent Organic Framework for Catalysis: Pd/COF-LZU1 in Suzuki–Miyaura Coupling Reaction
journal, December 2011

  • Ding, San-Yuan; Gao, Jia; Wang, Qiong
  • Journal of the American Chemical Society, Vol. 133, Issue 49
  • DOI: 10.1021/ja206846p

Charge Dynamics in A Donor-Acceptor Covalent Organic Framework with Periodically Ordered Bicontinuous Heterojunctions
journal, January 2013

  • Jin, Shangbin; Ding, Xuesong; Feng, Xiao
  • Angewandte Chemie International Edition, Vol. 52, Issue 7
  • DOI: 10.1002/anie.201209513

A Two-Dimensional Polymer from the Anthracene Dimer and Triptycene Motifs
journal, September 2013

  • Bhola, Radha; Payamyar, Payam; Murray, Daniel J.
  • Journal of the American Chemical Society, Vol. 135, Issue 38
  • DOI: 10.1021/ja404351p

Colloidal Covalent Organic Frameworks
journal, January 2017


A Belt-Shaped, Blue Luminescent, and Semiconducting Covalent Organic Framework
journal, November 2008

  • Wan, Shun; Guo, Jia; Kim, Jangbae
  • Angewandte Chemie International Edition, Vol. 47, Issue 46, p. 8826-8830
  • DOI: 10.1002/anie.200803826

A nanoporous two-dimensional polymer by single-crystal-to-single-crystal photopolymerization
journal, July 2014

  • Kissel, Patrick; Murray, Daniel J.; Wulftange, William J.
  • Nature Chemistry, Vol. 6, Issue 9
  • DOI: 10.1038/nchem.2008

Oriented Thin Films of a Benzodithiophene Covalent Organic Framework
journal, March 2014

  • Medina, Dana D.; Werner, Veronika; Auras, Florian
  • ACS Nano, Vol. 8, Issue 4
  • DOI: 10.1021/nn5000223

Two-Dimensional Polymers: Just a Dream of Synthetic Chemists?
journal, January 2009

  • Sakamoto, Junji; van Heijst, Jeroen; Lukin, Oleg
  • Angewandte Chemie International Edition, Vol. 48, Issue 6
  • DOI: 10.1002/anie.200801863

Observation of Rapid Exciton–Exciton Annihilation in Monolayer Molybdenum Disulfide
journal, September 2014

  • Sun, Dezheng; Rao, Yi; Reider, Georg A.
  • Nano Letters, Vol. 14, Issue 10
  • DOI: 10.1021/nl5021975

A Tetrathiafulvalene-Based Electroactive Covalent Organic Framework
journal, September 2014

  • Ding, Huimin; Li, Yonghai; Hu, Hui
  • Chemistry - A European Journal, Vol. 20, Issue 45
  • DOI: 10.1002/chem.201405330

Covalent Organic Frameworks Formed with Two Types of Covalent Bonds Based on Orthogonal Reactions
journal, January 2015

  • Zeng, Yongfei; Zou, Ruyi; Luo, Zhong
  • Journal of the American Chemical Society, Vol. 137, Issue 3
  • DOI: 10.1021/ja510926w

Enhancement of Chemical Stability and Crystallinity in Porphyrin-Containing Covalent Organic Frameworks by Intramolecular Hydrogen Bonds
journal, October 2013

  • Kandambeth, Sharath; Shinde, Digambar Balaji; Panda, Manas K.
  • Angewandte Chemie International Edition, Vol. 52, Issue 49
  • DOI: 10.1002/anie.201306775

Room Temperature Synthesis of Covalent–Organic Framework Films through Vapor-Assisted Conversion
journal, January 2015

  • Medina, Dana D.; Rotter, Julian M.; Hu, Yinghong
  • Journal of the American Chemical Society, Vol. 137, Issue 3
  • DOI: 10.1021/ja510895m

Kinematics of Exciton-Exciton Annihilation in Molecular Crystals
journal, February 1970


High-Rate Charge-Carrier Transport in Porphyrin Covalent Organic Frameworks: Switching from Hole to Electron to Ambipolar Conduction
journal, January 2012

  • Feng, Xiao; Liu, Lili; Honsho, Yoshihito
  • Angewandte Chemie International Edition, Vol. 51, Issue 11
  • DOI: 10.1002/anie.201106203

Synthesis of Metallophthalocyanine Covalent Organic Frameworks That Exhibit High Carrier Mobility and Photoconductivity
journal, December 2010

  • Ding, Xuesong; Guo, Jia; Feng, Xiao
  • Angewandte Chemie International Edition, Vol. 50, Issue 6
  • DOI: 10.1002/anie.201005919

A Photoconductive Covalent Organic Framework: Self-Condensed Arene Cubes Composed of Eclipsed 2D Polypyrene Sheets for Photocurrent Generation
journal, July 2009

  • Wan, Shun; Guo, Jia; Kim, Jangbae
  • Angewandte Chemie International Edition, Vol. 48, Issue 30
  • DOI: 10.1002/anie.200900881

A Photoconductive Thienothiophene-Based Covalent Organic Framework Showing Charge Transfer Towards Included Fullerene
journal, February 2013

  • Dogru, Mirjam; Handloser, Matthias; Auras, Florian
  • Angewandte Chemie International Edition, Vol. 52, Issue 10
  • DOI: 10.1002/anie.201208514

β-Ketoenamine-Linked Covalent Organic Frameworks Capable of Pseudocapacitive Energy Storage
journal, October 2013

  • DeBlase, Catherine R.; Silberstein, Katharine E.; Truong, Thanh-Tam
  • Journal of the American Chemical Society, Vol. 135, Issue 45
  • DOI: 10.1021/ja409421d

Rationally synthesized two-dimensional polymers
journal, May 2013

  • Colson, John W.; Dichtel, William R.
  • Nature Chemistry, Vol. 5, Issue 6
  • DOI: 10.1038/nchem.1628

Exceptional ammonia uptake by a covalent organic framework
journal, February 2010

  • Doonan, Christian J.; Tranchemontagne, David J.; Glover, T. Grant
  • Nature Chemistry, Vol. 2, Issue 3, p. 235-238
  • DOI: 10.1038/nchem.548

Oriented Films of Conjugated 2D Covalent Organic Frameworks as Photocathodes for Water Splitting
journal, December 2017

  • Sick, Torben; Hufnagel, Alexander G.; Kampmann, Jonathan
  • Journal of the American Chemical Society, Vol. 140, Issue 6
  • DOI: 10.1021/jacs.7b06081