Emissive Single-Crystalline Boroxine-Linked Colloidal Covalent Organic Frameworks

Austin M. Evans, Ioannina Castano, Alexandra Brumberg, Lucas R. Parent, Amanda R. Corcos, Rebecca L. Li, Nathan C. Flanders, David J. Gosztola, Nathan C. Gianneschi, Richard D. Schaller, William R. Dichtel

Research output: Contribution to journalArticle

Abstract

The synthesis of periodic two-dimensional (2D) polymers and characterization of their optoelectronic behaviors are challenges at the forefront of polymer chemistry and materials science. Recently, we showed that layered 2D polymers known as 2D covalent organic frameworks (COFs) can be synthesized as single crystals by preparing COF particles as colloidal suspensions. Here we expand this approach from the condensation of boronic acids and catechols to the dehydrative trimerization of polyboronic acids. The resulting boroxine-linked colloids are the next class of 2D COFs to be obtained as single-crystalline particles, as demonstrated here for four 2D COFs and one 3D COF. Colloidal stabilization enables detailed structural analysis by synchrotron X-ray diffraction and high-resolution transmission electron microscopy. Solution fluorescence spectroscopy revealed that the COF crystallites are highly emissive compared to their respective monomer solutions. Excitation-emission matrix fluorescence spectroscopy indicated that the origin of this enhanced emission can be attributed to through-space communication of chromophores between COF sheets. These observations will motivate the development of colloidal COF systems as a platform to organize functional aromatic systems into precise and predictable assemblies with emergent properties.

Original languageEnglish
JournalJournal of the American Chemical Society
DOIs
Publication statusAccepted/In press - Jan 1 2019

Fingerprint

Polymers
Fluorescence Spectrometry
Fluorescence spectroscopy
Crystalline materials
Catechols
Boronic Acids
Synchrotrons
Acids
Colloids
Materials science
Chromophores
High resolution transmission electron microscopy
Transmission Electron Microscopy
Crystallites
Structural analysis
X-Ray Diffraction
Optoelectronic devices
Condensation
Suspensions
Stabilization

ASJC Scopus subject areas

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

Cite this

Evans, A. M., Castano, I., Brumberg, A., Parent, L. R., Corcos, A. R., Li, R. L., ... Dichtel, W. R. (Accepted/In press). Emissive Single-Crystalline Boroxine-Linked Colloidal Covalent Organic Frameworks. Journal of the American Chemical Society. https://doi.org/10.1021/jacs.9b08815

Emissive Single-Crystalline Boroxine-Linked Colloidal Covalent Organic Frameworks. / Evans, Austin M.; Castano, Ioannina; Brumberg, Alexandra; Parent, Lucas R.; Corcos, Amanda R.; Li, Rebecca L.; Flanders, Nathan C.; Gosztola, David J.; Gianneschi, Nathan C.; Schaller, Richard D.; Dichtel, William R.

In: Journal of the American Chemical Society, 01.01.2019.

Research output: Contribution to journalArticle

Evans, AM, Castano, I, Brumberg, A, Parent, LR, Corcos, AR, Li, RL, Flanders, NC, Gosztola, DJ, Gianneschi, NC, Schaller, RD & Dichtel, WR 2019, 'Emissive Single-Crystalline Boroxine-Linked Colloidal Covalent Organic Frameworks', Journal of the American Chemical Society. https://doi.org/10.1021/jacs.9b08815
Evans, Austin M. ; Castano, Ioannina ; Brumberg, Alexandra ; Parent, Lucas R. ; Corcos, Amanda R. ; Li, Rebecca L. ; Flanders, Nathan C. ; Gosztola, David J. ; Gianneschi, Nathan C. ; Schaller, Richard D. ; Dichtel, William R. / Emissive Single-Crystalline Boroxine-Linked Colloidal Covalent Organic Frameworks. In: Journal of the American Chemical Society. 2019.
@article{74dd04bfc2434506aed3ee3422e67f6e,
title = "Emissive Single-Crystalline Boroxine-Linked Colloidal Covalent Organic Frameworks",
abstract = "The synthesis of periodic two-dimensional (2D) polymers and characterization of their optoelectronic behaviors are challenges at the forefront of polymer chemistry and materials science. Recently, we showed that layered 2D polymers known as 2D covalent organic frameworks (COFs) can be synthesized as single crystals by preparing COF particles as colloidal suspensions. Here we expand this approach from the condensation of boronic acids and catechols to the dehydrative trimerization of polyboronic acids. The resulting boroxine-linked colloids are the next class of 2D COFs to be obtained as single-crystalline particles, as demonstrated here for four 2D COFs and one 3D COF. Colloidal stabilization enables detailed structural analysis by synchrotron X-ray diffraction and high-resolution transmission electron microscopy. Solution fluorescence spectroscopy revealed that the COF crystallites are highly emissive compared to their respective monomer solutions. Excitation-emission matrix fluorescence spectroscopy indicated that the origin of this enhanced emission can be attributed to through-space communication of chromophores between COF sheets. These observations will motivate the development of colloidal COF systems as a platform to organize functional aromatic systems into precise and predictable assemblies with emergent properties.",
author = "Evans, {Austin M.} and Ioannina Castano and Alexandra Brumberg and Parent, {Lucas R.} and Corcos, {Amanda R.} and Li, {Rebecca L.} and Flanders, {Nathan C.} and Gosztola, {David J.} and Gianneschi, {Nathan C.} and Schaller, {Richard D.} and Dichtel, {William R.}",
year = "2019",
month = "1",
day = "1",
doi = "10.1021/jacs.9b08815",
language = "English",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",

}

TY - JOUR

T1 - Emissive Single-Crystalline Boroxine-Linked Colloidal Covalent Organic Frameworks

AU - Evans, Austin M.

AU - Castano, Ioannina

AU - Brumberg, Alexandra

AU - Parent, Lucas R.

AU - Corcos, Amanda R.

AU - Li, Rebecca L.

AU - Flanders, Nathan C.

AU - Gosztola, David J.

AU - Gianneschi, Nathan C.

AU - Schaller, Richard D.

AU - Dichtel, William R.

PY - 2019/1/1

Y1 - 2019/1/1

N2 - The synthesis of periodic two-dimensional (2D) polymers and characterization of their optoelectronic behaviors are challenges at the forefront of polymer chemistry and materials science. Recently, we showed that layered 2D polymers known as 2D covalent organic frameworks (COFs) can be synthesized as single crystals by preparing COF particles as colloidal suspensions. Here we expand this approach from the condensation of boronic acids and catechols to the dehydrative trimerization of polyboronic acids. The resulting boroxine-linked colloids are the next class of 2D COFs to be obtained as single-crystalline particles, as demonstrated here for four 2D COFs and one 3D COF. Colloidal stabilization enables detailed structural analysis by synchrotron X-ray diffraction and high-resolution transmission electron microscopy. Solution fluorescence spectroscopy revealed that the COF crystallites are highly emissive compared to their respective monomer solutions. Excitation-emission matrix fluorescence spectroscopy indicated that the origin of this enhanced emission can be attributed to through-space communication of chromophores between COF sheets. These observations will motivate the development of colloidal COF systems as a platform to organize functional aromatic systems into precise and predictable assemblies with emergent properties.

AB - The synthesis of periodic two-dimensional (2D) polymers and characterization of their optoelectronic behaviors are challenges at the forefront of polymer chemistry and materials science. Recently, we showed that layered 2D polymers known as 2D covalent organic frameworks (COFs) can be synthesized as single crystals by preparing COF particles as colloidal suspensions. Here we expand this approach from the condensation of boronic acids and catechols to the dehydrative trimerization of polyboronic acids. The resulting boroxine-linked colloids are the next class of 2D COFs to be obtained as single-crystalline particles, as demonstrated here for four 2D COFs and one 3D COF. Colloidal stabilization enables detailed structural analysis by synchrotron X-ray diffraction and high-resolution transmission electron microscopy. Solution fluorescence spectroscopy revealed that the COF crystallites are highly emissive compared to their respective monomer solutions. Excitation-emission matrix fluorescence spectroscopy indicated that the origin of this enhanced emission can be attributed to through-space communication of chromophores between COF sheets. These observations will motivate the development of colloidal COF systems as a platform to organize functional aromatic systems into precise and predictable assemblies with emergent properties.

UR - http://www.scopus.com/inward/record.url?scp=85076251309&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85076251309&partnerID=8YFLogxK

U2 - 10.1021/jacs.9b08815

DO - 10.1021/jacs.9b08815

M3 - Article

C2 - 31743009

AN - SCOPUS:85076251309

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

ER -