Two-dimensional sp2 carbon–conjugated covalent organic frameworks

Jin, Enquan; Asada, Mizue; Xu, Qing; Dalapati, Sasanka; Addicoat, Matthew A.; Brady, Michael A.; Xu, Hong; Nakamura, Toshikazu; Heine, Thomas; Chen, Qiuhong; Jiang, Donglin

doi:10.1126/science.aan0202

Two-dimensional sp² carbon–conjugated covalent organic frameworks

Journal Article · Thu Aug 17 00:00:00 EDT 2017 · Science

DOI:https://doi.org/10.1126/science.aan0202· OSTI ID:1379913

^[1]; ^[2]; ^[1]; ^[1]; ^[3]; ^[4]; ^[5]; Nakamura, Toshikazu ^[2]; ^[6]; Chen, Qiuhong ^[1]; ^[1]

Japan Advanced Inst. of Science and Technology, Asahidai (Japan)
Inst. for Molecular Science, Nishigo-naka, Myodaiji (Japan)
Nottingham Trent Univ., Nottingham (United Kingdom)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS). Molecular Foundry
Japan Advanced Inst. of Science and Technology, Asahidai (Japan); Inst. for Molecular Science, Nishigo-naka, Myodaiji (Japan)
Leipzig Univ. (Germany). Wilhelm-Ostwald-Inst. for Physical and Theoretical Chemistry

In this work, we synthesized a two-dimensional (2D) crystalline covalent organic framework (sp²c-COF) that was designed to be fully π-conjugated and constructed from all sp² carbons by C=C condensation reactions of tetrakis(4-formylphenyl)pyrene and 1,4-phenylenediacetonitrile. The C=C linkages topologically connect pyrene knots at regular intervals into a 2D lattice with π conjugations extended along both x and y directions and develop an eclipsed layer framework rather than the more conventionally obtained disordered structures. The sp²c-COF is a semiconductor with a discrete band gap of 1.9 electron volts and can be chemically oxidized to enhance conductivity by 12 orders of magnitude. The generated radicals are confined on the pyrene knots, enabling the formation of a paramagnetic carbon structure with high spin density. The sp² carbon framework induces ferromagnetic phase transition to develop spin-spin coherence and align spins unidirectionally across the material.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); European Research Council (ERC); Ministry of Education, Culture, Sports, Science and Technology, Japan

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1379913

Journal Information:: Science, Journal Name: Science Journal Issue: 6352 Vol. 357; ISSN 0036-8075

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

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