Design and synthesis of two-dimensional covalent organic frameworks with four-arm cores: Prediction of remarkable ambipolar charge-transport properties

Simil Thomas, Hong Li, Raghunath R. Dasari, Austin M. Evans, Ioannina Castano, Taylor G. Allen, Obadiah G. Reid, Garry Rumbles, William R. Dichtel, Nathan C. Gianneschi, Seth R. Marder, Veaceslav Coropceanu, Jean Luc Brédas

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

We have considered three two-dimensional (2D) π-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 π-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 π-conjugation.

Original languageEnglish
Pages (from-to)1868-1876
Number of pages9
JournalMaterials Horizons
Volume6
Issue number9
DOIs
Publication statusPublished - Nov 2019

Fingerprint

Porphyrins
Transport properties
Charge transfer
Zinc
Hole mobility
Semiconducting organic compounds
Electron mobility
Conjugated polymers
Photoconductivity
Photolysis
High resolution transmission electron microscopy
Valence bands
Conduction bands
X ray powder diffraction
Electronic structure
Density functional theory
Pyrene
Microwaves
Electrons
zinc hematoporphyrin

ASJC Scopus subject areas

  • Materials Science(all)
  • Mechanics of Materials
  • Process Chemistry and Technology
  • Electrical and Electronic Engineering

Cite this

Design and synthesis of two-dimensional covalent organic frameworks with four-arm cores : Prediction of remarkable ambipolar charge-transport properties. / Thomas, Simil; Li, Hong; Dasari, Raghunath R.; Evans, Austin M.; Castano, Ioannina; Allen, Taylor G.; Reid, Obadiah G.; Rumbles, Garry; Dichtel, William R.; Gianneschi, Nathan C.; Marder, Seth R.; Coropceanu, Veaceslav; Brédas, Jean Luc.

In: Materials Horizons, Vol. 6, No. 9, 11.2019, p. 1868-1876.

Research output: Contribution to journalArticle

Thomas, S, Li, H, Dasari, RR, Evans, AM, Castano, I, Allen, TG, Reid, OG, Rumbles, G, Dichtel, WR, Gianneschi, NC, Marder, SR, Coropceanu, V & Brédas, JL 2019, 'Design and synthesis of two-dimensional covalent organic frameworks with four-arm cores: Prediction of remarkable ambipolar charge-transport properties', Materials Horizons, vol. 6, no. 9, pp. 1868-1876. https://doi.org/10.1039/c9mh00035f
Thomas, Simil ; Li, Hong ; Dasari, Raghunath R. ; Evans, Austin M. ; Castano, Ioannina ; Allen, Taylor G. ; Reid, Obadiah G. ; Rumbles, Garry ; Dichtel, William R. ; Gianneschi, Nathan C. ; Marder, Seth R. ; Coropceanu, Veaceslav ; Brédas, Jean Luc. / Design and synthesis of two-dimensional covalent organic frameworks with four-arm cores : Prediction of remarkable ambipolar charge-transport properties. In: Materials Horizons. 2019 ; Vol. 6, No. 9. pp. 1868-1876.
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