Hexaazatriphenylene-Based Two-Dimensional Conductive Covalent Organic Framework with Anisotropic Charge Transfer

Seong-Wook Kim; Hyeonjung Jung; Mahmut Sait Okyay; Hyuk-Jun Noh; Sein Chung; Young Hyun Kim; Jong-Pil Jeon; Bryan M Wong; Kilwon Cho; Jeong-Min Seo; Jung-Woo Yoo; Jong-Beom Baek

doi:10.1002/anie.202310560

Hexaazatriphenylene-Based Two-Dimensional Conductive Covalent Organic Framework with Anisotropic Charge Transfer

Angew Chem Int Ed Engl. 2023 Oct 16;62(42):e202310560. doi: 10.1002/anie.202310560. Epub 2023 Sep 13.

Authors

Affiliations

¹ Department of Energy and Chemical Engineering/, Center for Dimension-Controllable Organic Frameworks, Ulsan National Institute of Science and Technology (UNIST), Ulsan, 44919, Republic of Korea.
² School of Materials Science and Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan, 44919, Republic of Korea.
³ Materials Science & Engineering Program, Department of Chemistry, and Department of Physics & Astronomy, University of California-Riverside, Riverside, CA, 92521, USA.
⁴ Department of Chemistry, Dartmouth College, Hanover, NH, 03755, USA.
⁵ Department of Chemical Engineering, Pohang University of Science and Technology, Pohang, 37673, Republic of Korea.
⁶ School of Materials Science and Engineering/, Graduate School of Semiconductor Materials and Devices, Ulsan National Institute of Science and Technology (UNIST), Ulsan, 44919, Republic of Korea.

PMID: 37654107
DOI: 10.1002/anie.202310560

Abstract

The development of covalent organic frameworks (COFs) with efficient charge transport is of immense interest for applications in optoelectronic devices. To enhance COF charge transport properties, electroactive building blocks and dopants can be used to induce extended conduction channels. However, understanding their intricate interplay remains challenging. We designed and synthesized a tailor-made COF structure with electroactive hexaazatriphenylene (HAT) core units and planar dioxin (D) linkages, denoted as HD-COF. With the support of theoretical calculations, we found that the HAT units in the HD-COF induce strong, eclipsed π-π stacking. The unique stacking of HAT units and the weak in-plane conjugation of dioxin linkages leads to efficient anisotropic charge transport. We fabricated HD-COF films to minimize the grain boundary effect of bulk COFs, which resulted in enhanced conductivity. As a result, the HD-COF films showed an electrical conductivity as high as 1.25 S cm^-1 after doping with tris(4-bromophenyl)ammoniumyl hexachloroantimonate.

Keywords: Anisotropic Charge Transfer; Conductivity; Covalent Organic Frameworks; Doping.

Abstract

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