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Title: Design and Synthesis of Two-Dimensional Covalent Organic Frameworks with Four-Arm Cores: Prediction of Remarkable Ambipolar Charge-Transport Properties

Abstract

We have considered three two-dimensional (2D) p-conjugated polymer network (i.e., covalent organic frameworks, COFs) materials based on pyrene, porphyrin, and zinc-porphyrin cores connected via diacetylenic linkers. Their electronic structures, investigated at the density functional theory global-hybrid level, are indicative of valence and conduction bands that have large widths, ranging between 1 and 2 eV. Using a molecular approach to derive the electronic couplings between adjacent core units and the electron-vibration couplings, the three p-conjugated 2D COFs are predicted to have ambipolar charge-transport characteristics with electron and hole mobilities in the range of 65-95 cm2 V-1 s-1. Such predicted values rank these 2D COFs among the highest-mobility organic semiconductors. In addition, we have synthesized the zinc-porphyrin based 2D COF and carried out structural characterization via powder X-ray diffraction, high-resolution transmission electron microscopy, and surface area analysis, which demonstrates the feasibility of these electroactive networks. Steady-state and flash-photolysis time-resolved microwave conductivity measurements on the zinc-porphyrin COF point to appreciable, broadband photoconductivity while transmission spectral measurements are indicative of extended p-conjugation.

Authors:
 [1];  [1];  [1];  [2];  [2];  [3];  [3]; ORCiD logo [3];  [2];  [2];  [1];  [1];  [1]
  1. Georgia Institute of Technology
  2. Northwestern University
  3. National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1573204
Report Number(s):
NREL/JA-5900-75308
DOE Contract Number:  
AC36-08GO28308
Resource Type:
Journal Article
Journal Name:
Materials Horizons
Additional Journal Information:
Journal Volume: 6; Journal Issue: 9
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; conjugated polymers; couplings; density functional theory; electronic structure; photolysis; porphyrins

Citation Formats

Thomas, Simil, Li, Hong, Dasari, Raghunath R., Evans, Austin M., Castano, Ioannina, Allen, Taylor, Reid, Obadiah G, Rumbles, Garry, Dichtel, William R., Gianneschi, Nathan C., Marder, Seth R., Coropceanu, Veaceslav, and Bredas, Jean-Luc. Design and Synthesis of Two-Dimensional Covalent Organic Frameworks with Four-Arm Cores: Prediction of Remarkable Ambipolar Charge-Transport Properties. United States: N. p., 2019. Web. doi:https://dx.doi.org/10.1039/C9MH00035F.
Thomas, Simil, Li, Hong, Dasari, Raghunath R., Evans, Austin M., Castano, Ioannina, Allen, Taylor, Reid, Obadiah G, Rumbles, Garry, Dichtel, William R., Gianneschi, Nathan C., Marder, Seth R., Coropceanu, Veaceslav, & Bredas, Jean-Luc. Design and Synthesis of Two-Dimensional Covalent Organic Frameworks with Four-Arm Cores: Prediction of Remarkable Ambipolar Charge-Transport Properties. United States. doi:https://dx.doi.org/10.1039/C9MH00035F.
Thomas, Simil, Li, Hong, Dasari, Raghunath R., Evans, Austin M., Castano, Ioannina, Allen, Taylor, Reid, Obadiah G, Rumbles, Garry, Dichtel, William R., Gianneschi, Nathan C., Marder, Seth R., Coropceanu, Veaceslav, and Bredas, Jean-Luc. Wed . "Design and Synthesis of Two-Dimensional Covalent Organic Frameworks with Four-Arm Cores: Prediction of Remarkable Ambipolar Charge-Transport Properties". United States. doi:https://dx.doi.org/10.1039/C9MH00035F.
@article{osti_1573204,
title = {Design and Synthesis of Two-Dimensional Covalent Organic Frameworks with Four-Arm Cores: Prediction of Remarkable Ambipolar Charge-Transport Properties},
author = {Thomas, Simil and Li, Hong and Dasari, Raghunath R. and Evans, Austin M. and Castano, Ioannina and Allen, Taylor and Reid, Obadiah G and Rumbles, Garry and Dichtel, William R. and Gianneschi, Nathan C. and Marder, Seth R. and Coropceanu, Veaceslav and Bredas, Jean-Luc},
abstractNote = {We have considered three two-dimensional (2D) p-conjugated polymer network (i.e., covalent organic frameworks, COFs) materials based on pyrene, porphyrin, and zinc-porphyrin cores connected via diacetylenic linkers. Their electronic structures, investigated at the density functional theory global-hybrid level, are indicative of valence and conduction bands that have large widths, ranging between 1 and 2 eV. Using a molecular approach to derive the electronic couplings between adjacent core units and the electron-vibration couplings, the three p-conjugated 2D COFs are predicted to have ambipolar charge-transport characteristics with electron and hole mobilities in the range of 65-95 cm2 V-1 s-1. Such predicted values rank these 2D COFs among the highest-mobility organic semiconductors. In addition, we have synthesized the zinc-porphyrin based 2D COF and carried out structural characterization via powder X-ray diffraction, high-resolution transmission electron microscopy, and surface area analysis, which demonstrates the feasibility of these electroactive networks. Steady-state and flash-photolysis time-resolved microwave conductivity measurements on the zinc-porphyrin COF point to appreciable, broadband photoconductivity while transmission spectral measurements are indicative of extended p-conjugation.},
doi = {https://dx.doi.org/10.1039/C9MH00035F},
journal = {Materials Horizons},
number = 9,
volume = 6,
place = {United States},
year = {2019},
month = {5}
}

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