Synthesis, Hole Doping, and Electrical Properties of a Semiconducting Azatriangulene-Based Covalent Organic Framework

Burke, David W.; Dasari, Raghunath R.; Sangwan, Vinod K.; Oanta, Alexander K.; Hirani, Zoheb; Pelkowski, Chloe E.; Tang, Yongjian; Li, Ruofan; Ralph, Daniel C.; Hersam, Mark C.; Barlow, Stephen; Marder, Seth R.; Dichtel, William R.

doi:10.1021/jacs.2c12371

Synthesis, Hole Doping, and Electrical Properties of a Semiconducting Azatriangulene-Based Covalent Organic Framework

Journal Article · Mon May 22 00:00:00 EDT 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.2c12371· OSTI ID:2203549

Burke, David W. ^[1]; ^[2]; ^[3]; Oanta, Alexander K. ^[3]; ^[3]; Pelkowski, Chloe E. ^[4]; Tang, Yongjian ^[5]; ^[5]; ^[5]; ^[3]; ^[6]; ^[6]; ^[3]

Northwestern University, Evanston, IL (United States); Cornell University
Georgia Institute of Technology, Atlanta, GA (United States)
Northwestern University, Evanston, IL (United States)
Northwestern University, Evanston, IL (United States); Georgia Institute of Technology, Atlanta, GA (United States)
Cornell University, Ithaca, NY (United States)
Georgia Institute of Technology, Atlanta, GA (United States); University of Colorado Boulder, CO (United States)

Two-dimensional covalent organic frameworks (2D COFs) containing heterotriangulenes have been theoretically identified as semiconductors with tunable, Dirac-cone-like band structures, which are expected to afford high charge-carrier mobilities ideal for next-generation flexible electronics. However, few bulk syntheses of these materials have been reported, and existing synthetic methods provide limited control of network purity and morphology. Here, we report transimination reactions between benzophenone-imine-protected azatriangulenes (OTPA) and benzodithiophene dialdehydes (BDT), which afforded a new semiconducting COF network, OTPA-BDT. The COFs were prepared as both polycrystalline powders and thin films with controlled crystallite orientation. Here, the azatriangulene nodes are readily oxidized to stable radical cations upon exposure to an appropriate p type dopant, tris(4-bromophenyl)ammoniumyl hexachloroantimonate, after which the network’s crystallinity and orientation are maintained. Oriented, hole-doped OTPA-BDT COF films exhibit electrical conductivities of up to 1.2 × 10^–1 S cm^–1, which are among the highest reported for imine-linked 2D COFs to date.

View Accepted Manuscript (DOE)

Research Organization:: Cornell University, Ithaca, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); Army Research Office (ARO); Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource; Northwestern University Materials Research Science and Engineering Center (MRSEC); National Science Foundation (NSF)

Grant/Contract Number:: SC0017671; AC02-06CH11357; SC0012704

OSTI ID:: 2203549

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 22 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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