Research ArticleChemistry

Multiple heteroatom substitution to graphene nanoribbon

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Science Advances  13 Apr 2018:
Vol. 4, no. 4, eaar7181
DOI: 10.1126/sciadv.aar7181
  • Fig. 1 Synthesis of multiple heteroatom-substituted GNR.

    (A) Schematic drawing of 5-(10-chloroanthracen-9-yl)-10-(10-iodoanthracen-9-yl)-5,10-dihydrodibenzo[b,e][1,4]azaborinine. (B) On-surface reaction paths of long- and (C) short-periodicity boron-nitrogen GNRs (BN-GNR). Gray and purple triangles indicate boron- and nitrogen-centered membered rings, respectively. (D) STM topography of the synthesized BN-GNR on Au(111). (E and F) Corresponding AFM images. Measurement parameters: Vtip = −200 mV and I = 0.8 pA in (D). Vtip = 0 mV and A = 60 pm in (E) and (F).

  • Fig. 2 AFM results of BN-GNR.

    (A) Simulated atomic structure from above (left) and to the side (right), with carbon atoms shown in cyan, gold in yellow, boron in blue, nitrogen in green, and hydrogen in white. (B) Simulated AFM images at decreasing tip height. (C to J) Series of high-resolution AFM images taken at different Z distances. (K) Force spectroscopic measurements taken at different elements in the BN-GNR. (L) Close view. (M) Calculated frequency change (Δf) over labeled atomic sites as a function of tip-surface distance (note that this is referenced to the fixed part of the tip, and the effective distance is about 4.0 Å smaller once the CO molecule is included). Measurement parameters: Vtip = 0 mV and A = 60 pm.

  • Fig. 3 Apparent bond analysis.

    (A) Analysis of the bond lengths in the AFM image. (B) Calculated valence electron density (at an isocontour of 1.0 eÅ−3).

  • Fig. 4 Electronic structure of BN-GNR.

    (A) STM topography and (B) the corresponding AFM image. STS taken at the center in (C) and the edge in (D). CBE, conduction band edge. Six different positions were measured as labeled in (A). (E to L) Series of constant height dI/dV maps measured with a lock-in amplifier (root mean square amplitude = 14 mV and frequency = 512 Hz) at the different bias voltages. Arrows indicate the positions of the STS measurements. (M) Simulated STM topographies at a bias of −1.0 V (left) and +1.5 V (right). (N) Calculated DOS.

  • Table 1 Summary of apparent bond lengths.
    BondExperimentSimulationDFT calculation
    C1–C2142142145
    C3–N196196142
    B–C4135130138

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/4/4/eaar7181/DC1

    Supplementary Materials and Methods

    fig. S1. Examples of various couplings.

    fig. S2. Small boron-nitrogen codoped GNR.

    fig. S3. Boron-nitrogen codoped GNR with a low-doped density.

    fig. S4. Simulated BN-GNR structures, spectra, and electronic parameters.

    fig. S5. Force extraction.

    fig. S6. Simulated charge analysis.

    fig. S7. Simple model calculation analysis based on Lennard-Jones potential as E(Z) = 4ε[ (σ/Z)12 − (σ/Z)6].

    fig. S8. Synthesis of BN-GNR precursor.

    fig. S9. Chemical structure of 9-bromo-10-chloroanthracene.

    fig. S10. Chemical structure of N-(2-bromophenyl)-N-phenyl-10-chloroanthracen-9-amine (2).

    fig. S11. 1H NMR spectrum of 2 in CDCl3 at 25°C.

    fig. S12. 13C NMR spectrum of 2 in CDCl3 at 25°C.

    fig. S13. Chemical structure of 5-(10-chloroanthracen-9-yl)-10-(10-iodoanthracen-9-yl)-5,10-dihydrodibenzo[b,e][1,4]azaborinine (1).

    fig. S14. 1H NMR spectrum of 1 in CS2/CDCl3 (=2/1) at 45°C.

    fig. S15. 13C NMR spectrum of 1 in CS2/CDCl3 (=2/1) at 45°C.

    fig. S16. 11B NMR spectrum of 1 in CS2/CDCl3 (=2/1) at 45°C.

    References (6163)

  • Supplementary Materials

    This PDF file includes:

    • Supplementary Materials and Methods
    • fig. S1. Examples of various couplings.
    • fig. S2. Small boron-nitrogen codoped GNR.
    • fig. S3. Boron-nitrogen codoped GNR with a low-doped density.
    • fig. S4. Simulated BN-GNR structures, spectra, and electronic parameters.
    • fig. S5. Force extraction.
    • fig. S6. Simulated charge analysis.
    • fig. S7. Simple model calculation analysis based on Lennard-Jones potential as E(Z) = 4ε (σ/Z)12 − (σ/Z)6.
    • fig.S8. Synthesis of BN-GNR precursor.
    • fig. S9. Chemical structure of 9-bromo-10-chloroanthracene.
    • fig. S10. Chemical structure of N-(2-bromophenyl)-N-phenyl-10-chloroanthracen-9-amine (2).
    • fig. S11. 1H NMR spectrum of 2 in CDCl3 at 25°C.
    • fig. S12. 13C NMR spectrum of 2 in CDCl3 at 25°C.
    • fig. S13. Chemical structure of 5-(10-chloroanthracen-9-yl)-10-(10-iodoanthracen-9-yl)-5,10-dihydrodibenzob,e1,4azaborinine (1).
    • fig. S14. 1H NMR spectrum of 1 in CS2/CDCl3 (=2/1) at 45°C.
    • fig. S15. 13C NMR spectrum of 1 in CS2/CDCl3 (=2/1) at 45°C.
    • fig. S16. 11B NMR spectrum of 1 in CS2/CDCl3 (=2/1) at 45°C.
    • References (61–63)

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