Two-dimensional sp2 carbon–conjugated covalent organic frameworks

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

doi:10.1126/science.aan0202

Two-dimensional sp² carbon–conjugated covalent organic frameworks

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

611 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	673-676
Number of pages	4
Journal	Science
Volume	357
Issue number	6352
DOIs	https://doi.org/10.1126/science.aan0202
Publication status	Published - 2017 Aug 18

Bibliographical note

Funding Information:
E.J. acknowledges Chinese Scholarship Concert for financial support for his study in Japan. S.D. is now an international research fellow of the Japan Society for the Promotion of Science. M.A.B. acknowledges the Advanced Light Source, which is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under contract DE-AC02-05CH11231. T.H. and M.A. acknowledge supercomputer time at ZIH Dresden and financial support by the European Research Council (grant ERC-StG 256962 C3ENV) and the VolkswagenStiftung. D.J. acknowledges a Grant-in-Aid for Scientific Research (A) (17H01218) from the Ministry of Education, Culture, Sports, Science and Technology, Japan, and support from the ENEOS Hydrogen Trust Fund and the Ogasawara Foundation for the Promotion of Science and Engineering. D.J. conceived and designed the project. E.J., Q.X., S.D., H.X., and Q.C. conducted the experiments. M.A.A. and T.H. conducted DFTB calculations and structure simulations. M.A. and T.N. conducted ESR and SQUID measurements. M.A.B. conducted WAXS measurements. D.J., E.J., Q.C., and S.D. wrote the manuscript and discussed the results with all authors. All data are reported in the main text and supplementary materials.

Publisher Copyright:
© 2017, American Association for the Advancement of Science. All rights reserved.

All Science Journal Classification (ASJC) codes

General

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10.1126/science.aan0202

Cite this

@article{d2568bbaface499ea5d2c1fc449e3d61,

title = "Two-dimensional sp2 carbon–conjugated covalent organic frameworks",

abstract = "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.",

author = "Enquan Jin and Mizue Asada and Qing Xu and Sasanka Dalapati and Addicoat, {Matthew A.} and Brady, {Michael A.} and Hong Xu and Toshikazu Nakamura and Thomas Heine and Qiuhong Chen and Donglin Jiang",

note = "Funding Information: E.J. acknowledges Chinese Scholarship Concert for financial support for his study in Japan. S.D. is now an international research fellow of the Japan Society for the Promotion of Science. M.A.B. acknowledges the Advanced Light Source, which is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under contract DE-AC02-05CH11231. T.H. and M.A. acknowledge supercomputer time at ZIH Dresden and financial support by the European Research Council (grant ERC-StG 256962 C3ENV) and the VolkswagenStiftung. D.J. acknowledges a Grant-in-Aid for Scientific Research (A) (17H01218) from the Ministry of Education, Culture, Sports, Science and Technology, Japan, and support from the ENEOS Hydrogen Trust Fund and the Ogasawara Foundation for the Promotion of Science and Engineering. D.J. conceived and designed the project. E.J., Q.X., S.D., H.X., and Q.C. conducted the experiments. M.A.A. and T.H. conducted DFTB calculations and structure simulations. M.A. and T.N. conducted ESR and SQUID measurements. M.A.B. conducted WAXS measurements. D.J., E.J., Q.C., and S.D. wrote the manuscript and discussed the results with all authors. All data are reported in the main text and supplementary materials. Publisher Copyright: {\textcopyright} 2017, American Association for the Advancement of Science. All rights reserved.",

year = "2017",

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T1 - Two-dimensional sp2 carbon–conjugated covalent organic frameworks

AU - Jin, Enquan

AU - Asada, Mizue

AU - Xu, Qing

AU - Dalapati, Sasanka

AU - Addicoat, Matthew A.

AU - Brady, Michael A.

AU - Xu, Hong

AU - Nakamura, Toshikazu

AU - Heine, Thomas

AU - Chen, Qiuhong

AU - Jiang, Donglin

N1 - Funding Information: E.J. acknowledges Chinese Scholarship Concert for financial support for his study in Japan. S.D. is now an international research fellow of the Japan Society for the Promotion of Science. M.A.B. acknowledges the Advanced Light Source, which is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under contract DE-AC02-05CH11231. T.H. and M.A. acknowledge supercomputer time at ZIH Dresden and financial support by the European Research Council (grant ERC-StG 256962 C3ENV) and the VolkswagenStiftung. D.J. acknowledges a Grant-in-Aid for Scientific Research (A) (17H01218) from the Ministry of Education, Culture, Sports, Science and Technology, Japan, and support from the ENEOS Hydrogen Trust Fund and the Ogasawara Foundation for the Promotion of Science and Engineering. D.J. conceived and designed the project. E.J., Q.X., S.D., H.X., and Q.C. conducted the experiments. M.A.A. and T.H. conducted DFTB calculations and structure simulations. M.A. and T.N. conducted ESR and SQUID measurements. M.A.B. conducted WAXS measurements. D.J., E.J., Q.C., and S.D. wrote the manuscript and discussed the results with all authors. All data are reported in the main text and supplementary materials. Publisher Copyright: © 2017, American Association for the Advancement of Science. All rights reserved.

PY - 2017/8/18

Y1 - 2017/8/18

N2 - 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.

AB - 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.

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