Research ArticleMATERIALS SCIENCE

Readily accessible shape-memory effect in a porous interpenetrated coordination network

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Science Advances  27 Apr 2018:
Vol. 4, no. 4, eaaq1636
DOI: 10.1126/sciadv.aaq1636
  • Fig. 1 The typical sorption isotherms associated with a shape-memory effect in an FMOM.

    The first adsorption cycle occurs in step(s), whereas desorption lacks any steps (left). The second and subsequent sorption cycles are examples of type I isotherms (right).

  • Fig. 2 Structure of X-pcu-3-Zn and its phase changes under external stimuli.

    A schematic illustration of the shape-memory effect in X-pcu-3-Zn-3i (left). The structure of X-pcu-3-Zn-3i is composed of axially coordinated L1 linkers that cross-link 2D square grids to form a 3D structure (right).

  • Fig. 3 In situ coincidence PXRD measurements.

    PXRD patterns for X-pcu-3-Zn-3i are correlated with adsorption and desorption isotherms for CO2 at 195 K (left), N2 at 77 K (middle), and CO at 82 K (right). a.u., arbitrary unit.

  • Fig. 4 Low- and high-pressure CO2 sorption on X-pcu-3-Zn.

    Ten consecutive cycles of CO2 sorption at 195 K (left). First cycle of high-pressure CO2 at 298 K (right).

  • Fig. 5 Structural insights for the three phases.

    The sql networks of the α, β, and γ forms of X-pcu-3-Zn-3i (top) and how three of these networks (red, green, and blue, respectively) interact through C–H···O (teal) and π···π (yellow) interactions (bottom).

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/4/4/eaaq1636/DC1

    fig. S1. Structure of the three phases.

    fig. S2. Diffraction pattern and single-crystal images.

    fig. S3. Low-pressure gas sorption.

    fig. S4. Recyclability of shape-memory phase at 195 K CO2.

    fig. S5. High-pressure CO2 sorption.

    fig. S6. In situ variable temperature PXRD.

    fig. S7. Solvent-induced phase change.

    fig. S8. PXRD data for X-pcu-3-Zn-3i-γ obtained from different experiments.

    fig. S9. Phase change from γ to α phase.

    fig. S10. Variable temperature PXRD of shape-memory phase.

    fig. S11. Distortion of paddlewheel MBB and orientation of X-ligands in X-pcu-3-Zn-3i-α.

    fig. S12. Distortion of paddlewheel MBB and orientation of X ligands in X-pcu-3-Zn-3i-β.

    fig. S13. Distortion of paddlewheel MBB and orientation of X ligands in X-pcu-3-Zn-3i-γ.

    fig. S14. Thermogravimetric analysis (TGA) profiles.

    fig. S15. Comparison of modeling and experimental isotherm.

    fig. S16. Free-energy difference.

    fig. S17. Chemically distinct atoms in X-pcu-3-Zn-3i-α.

    fig. S18. The chemically distinct atoms in X-pcu-3-Zn-3i-β.

    fig. S19. The chemically distinct atoms in X-pcu-3-Zn-3i-γ.

    table S1. Examples of previously reported FMOMs with large hysteresis.

    table S2. Crystal data and refinement parameters.

    table S3. Numerical labeling of atoms corresponds to fig. S17.

    table S4. The crystallographic distances (in Å) between various atoms in X-pcu-3-Zn-3i-α.

    table S5. The partial charges (in e) for the chemically distinct atoms in X-pcu-3-Zn-3i-β.

    table S6. The crystallographic distances (in Å) between various atoms in X-pcu-3-Zn-3i-β.

    table S7. Numerical labeling of atoms corresponds to fig. S18.

    table S8. Labels of atoms correspond to fig. S18.

    table S9. Calculated energies for three phases.

    References (4162)

  • Supplementary Materials

    This PDF file includes:

    • fig. S1. Structure of the three phases.
    • fig. S2. Diffraction pattern and single-crystal images.
    • fig. S3. Low-pressure gas sorption.
    • fig. S4. Recyclability of shape-memory phase at 195 K CO2.
    • fig. S5. High-pressure CO2 sorption.
    • fig. S6. In situ variable temperature PXRD.
    • fig. S7. Solvent-induced phase change.
    • fig. S8. PXRD data for X-pcu-3-Zn-3i-γ obtained from different experiments.
    • fig. S9. Phase change from γ to α phase.
    • fig. S10. Variable temperature PXRD of shape-memory phase.
    • fig. S11. Distortion of paddlewheel MBB and orientation of X-ligands in X-pcu-3-Zn-3i-α.
    • fig. S12. Distortion of paddlewheel MBB and orientation of X ligands in X-pcu-3-Zn-3i-β.
    • fig. S13. Distortion of paddlewheel MBB and orientation of X ligands in X-pcu-3-Zn-3i-γ.
    • fig. S14. Thermogravimetric analysis (TGA) profiles.
    • fig. S15. Comparison of modeling and experimental isotherm.
    • fig. S16. Free-energy difference.
    • fig. S17. Chemically distinct atoms in X-pcu-3-Zn-3i-α.
    • fig. S18. The chemically distinct atoms in X-pcu-3-Zn-3i-β.
      fig. S19. The chemically distinct atoms in X-pcu-3-Zn-3i-γ.
    • table S1. Examples of previously reported FMOMs with large hysteresis.
    • table S2. Crystal data and refinement parameters.
    • table S3. Numerical labeling of atoms corresponds to fig. S17.
    • table S4. The crystallographic distances (in Å) between various atoms in X-pcu-3-Zn-3i-α.
    • table S5. The partial charges (in e) for the chemically distinct atoms in X-pcu-3-Zn-3i-β.
    • table S6. The crystallographic distances (in Å) between various atoms in X-pcu-3-Zn-3i-β.
    • table S7. Numerical labeling of atoms corresponds to fig. S18.
    • table S8. Labels of atoms correspond to fig. S18.
    • table S9. Calculated energies for three phases.
    • References (41–62)

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