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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. Finally, 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.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Institutes of Health (NIH); National Science Foundation (NSF); US Army Research Office (ARO)
OSTI Identifier:
1630069
Grant/Contract Number:  
AC02-06CH11357; W911NF-15-1-0447; DGE-1324585; DMREF-1629383; DGE-1842165
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 50; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; covalent organic frameworks; monomers; nanoparticles; two dimensional materials; physical and chemical processes

Citation Formats

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., and Dichtel, William R.. Emissive Single-Crystalline Boroxine-Linked Colloidal Covalent Organic Frameworks. United States: N. p., 2019. Web. 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. United States. 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., and Dichtel, William R.. Tue . "Emissive Single-Crystalline Boroxine-Linked Colloidal Covalent Organic Frameworks". United States. https://doi.org/10.1021/jacs.9b08815. https://www.osti.gov/servlets/purl/1630069.
@article{osti_1630069,
title = {Emissive Single-Crystalline Boroxine-Linked Colloidal Covalent Organic Frameworks},
author = {Evans, Austin M. and Castano, Ioannina and Brumberg, Alexandra 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.},
abstractNote = {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. Finally, 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.},
doi = {10.1021/jacs.9b08815},
journal = {Journal of the American Chemical Society},
number = 50,
volume = 141,
place = {United States},
year = {2019},
month = {11}
}

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