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Lewis acid-catalysed formation of two-dimensional phthalocyanine covalent organic frameworks

Nature Chemistry volume 2, pages 672677 (2010) | Download Citation

Abstract

Covalent organic frameworks (COFs) offer a new strategy for assembling organic semiconductors into robust networks with atomic precision and long-range order. General methods for COF synthesis will allow complex building blocks to be incorporated into these emerging materials. Here we report a new Lewis acid-catalysed protocol to form boronate esters directly from protected catechols and arylboronic acids. This transformation also provides crystalline boronate ester-linked COFs from protected polyfunctional catechols and bis(boronic acids). Using this method, we prepared a new COF that features a square lattice composed of phthalocyanine macrocycles joined by phenylene bis(boronic acid) linkers. The phthalocyanines stack in an eclipsed fashion within the COF to form 2.3 nm pores that run parallel to the stacked chromophores. The material's broad absorbance over the solar spectrum, potential for efficient charge transport through the stacked phthalocyanines, good thermal stability and the modular nature of COF synthesis, show strong promise for applications in organic photovoltaic devices.

  • Compound C6H7BO2

    Phenylboronic acid

  • Compound C9H10O2

    2,2-Dimethyl-1,3-benzodioxole

  • Compound C12H9BO2

    2-Phenyl-1,3,2-benzodioxaborole

  • Compound C44H34N8O8

    2,2,10,10,18,18,26,26-Octamethyl-33H,35H-tetrakis[1,3]benzodioxolo[5,6-b:5',6'-g:5'',6''-l:5''',6'''-q]porphyrazine

  • Compound C6H8B2O4

    1,4-Benzenediboronic acid

  • Compound C9H8Br2O2

    5,6-Dibromo-2,2-dimethyl-1,3-benzodioxole

  • Compound C11H8N2O2

    2,2-Dimethyl-1,3-benzodioxole-5,6-dicarbonitrile

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Acknowledgements

This research was supported by start-up funds provided by Cornell University and the National Science Foundation (NSF)-funded Centers for Chemical Innovation Phase I Center for Molecular Interfacing (CHE-0847926). We also made use of the Cornell Center for Materials Research facilities with support from the NSF Materials Research Science and Engineering Centers program (DMR-0520404). E.L.S. acknowledges the award of the American Competitiveness in Chemistry postdoctoral fellowship from the NSF (CHE-0936988). We thank H. Sai and N. Hoepker for instrument assistance and A. Côté and A. Beeby for discussions.

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  1. Department of Chemistry and Chemical Biology, Cornell University, Baker Laboratory, Ithaca, New York 14853-1301, USA

    • Eric L. Spitler
    •  & William R. Dichtel

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Contributions

Both authors conceived the project, performed and interpreted the results of the experiments and wrote the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to William R. Dichtel.

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DOI

https://doi.org/10.1038/nchem.695

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