Science Advances

Supplementary Materials

This PDF file includes:

  • Section S1. Spectroscopic characterization of 1
  • Section S2. Voltammetry of 1
  • Section S3. UV-vis spectroscopy of 1 + varying buffers
  • Section S4. Homoconjugation
  • Section S5. Kinetic analysis
  • Section S6. Effective overpotential determination
  • Section S7. Selectivity for H2O versus H2O2
  • Section S8. Conceptual background for E1/2 and pKa scaling relationships
  • Section S9. Single crystal x-ray structure
  • Fig. S1. Full high-resolution ESI mass spectrum of 1 with identified peaks, as labeled.
  • Fig. S2. High-resolution ESI mass spectrum and isotopic fits for the M5+ + 3OTf ion.
  • Fig. S3. UV-vis spectrum of 1 in N,N′-dimethylformamide.
  • Fig. S4. IR spectrum of 1.
  • Fig. S5. A CV of an Ar-sparged solution of 1.
  • Fig. S6. Scan rate investigation of the FeIII/FeII redox couple of 1 in unbuffered solution.
  • Fig. S7. Voltammograms of an Ar-sparged solution of 1 before and after addition of buffered AcOH.
  • Fig. S8. Investigation of the FeIII/FeII redox couple of 1 with titrations of AcOH buffer.
  • Fig. S9. Scan rate investigation of the FeIII/FeII redox couple of 1 in AcOH-buffered solution.
  • Fig. S10. Investigation of the FeIII/FeII redox couple of 1 with titrations of BzOH buffer.
  • Fig. S11. Scan rate investigation of the FeIII/FeII redox couple of 1 in BzOH-buffered solution.
  • Fig. S12. Investigation of the FeIII/FeII redox couple of 1 with titrations of SalOH buffer.
  • Fig. S13. Scan rate investigation of the FeIII/FeII redox couple of 1 in SalOH-buffered solution.
  • Fig. S14. Investigation of the FeIII/FeII redox couple of 1 with titrations of TFA buffer.
  • Fig. S15. Scan rate investigation of the FeIII/FeII redox couple of 1 in TFA-buffered solution.
  • Fig. S16. Investigation of the FeIII/FeII redox couple of 1 with titrations of DMF-HOTf-buffer.
  • Fig. S17. Investigation of the FeIII/FeII redox couple of 1 with titrations of Lut-HBF4 buffer.
  • Fig. S18. Changes in E1/2(FeIII/FeII) with varying buffers (and concentrations).
  • Fig. S19. CVs of an O2-sparged MeCN solution containing 100 mM AcOH buffer before (black) and after (blue) adding 30 μM 1.
  • Fig. S20. Voltammograms of 1 with AcOH buffer under various solution conditions.
  • Fig. S21. Voltammograms of 1 with BzOH buffer under various solution conditions.
  • Fig. S22. Voltammograms of 1 with SalOH buffer under various solution conditions.
  • Fig. S23. Voltammograms of 1 with TFA buffer under various solution conditions.
  • Fig. S24. Voltammograms of 1 with Lut-H+ buffer under various solution conditions.
  • Fig. S25. Voltammograms of 1 with DMF-HOTf buffer under various solution conditions.
  • Fig. S26. Rinse tests for all of the buffers used in this study.
  • Fig. S27. UV-vis spectra of MeCN solutions containing 1 (~0.05 mM), n-Bu4NBF4 (~0.05 M), and varying 1:1 buffers (~0.05 M, as identified).
  • Fig. S28. Foot-of-the-wave analysis for the buffer concentrations used in this study (all at 1 atm O2).
  • Fig. S29. Foot-of-the-wave analysis for all the partial pressure O2 measurements performed in this study (all at 20 mM buffer).
  • Fig. S30. TOFmax versus substrate plots for the buffers used in this study.
  • Fig. S31. Plot of kobs versus partial pressure of O2 for each of the buffers used in this study.
  • Fig. S32. RRDE analysis using ferrocene to estimate collection efficiencies.
  • Fig. S33. RRDE analysis for the ORR catalyzed by 1 using DMF-HOTf buffer.
  • Fig. S34. RRDE analysis for the ORR catalyzed by 1 using TFAH buffer.
  • Fig. S35. RRDE analysis for the ORR catalyzed by 1 using SalOH buffer.
  • Fig. S36. RRDE analysis for the ORR catalyzed by 1 and BzOH buffer.
  • Fig. S37. RRDE analysis for the ORR catalyzed by 1 and AcOH buffer.
  • Fig. S38. The complete x-ray model of Fe-o-TMAOTf5•2H2O represented with balls and sticks.
  • Fig. S39. The complete numbering scheme of the cation-only portion of Fe-o-TMAOTf5•2H2O with 50% thermal ellipsoid probability levels.
  • Fig. S40. The x-ray model of the cation-only portion of Fe-o-TMAOTf5•2H2O from a secondary perspective showing the αβαβ isomer of porphyrin structure.
  • Fig. S41. The complete numbering of the disordered triflate at a general position in the model of Fe-o-TMAOTf5•2H2O with 50% thermal ellipsoid probability levels.
  • Fig. S42. The unit cell of Fe-o-TMAOTf5•2H2O, with a surface that represents a level of 1.5 e/Å3.
  • Fig. S43. All orientations of the disordered triflate are shown in relation to the 4¯ rotation axis, represented with red lines.
  • Table S1. Summary of E1/2(FeIII/FeII) (V) versus Fc+/Fc values measured under the conditions reported in this study; errors are ±0.005 V.
  • Table S2. Q-band region λmax values for ~0.05 mM 1 in MeCN containing ~0.05 M n-Bu4NBF4 and ~0.05 M buffer.
  • Table S3. Homoconjugation formation constants for the buffers used in this study.
  • Table S4. Calculated values for nonhomoconjugated acid and conjugate base (HAfree = Afree and HB+free = Bfree) for varying buffer identities and concentrations.
  • Table S5. Average percent H2O2 formed for 1-catalyzed ORR in MeCN containing various buffers.
  • Table S6. Crystal data and structure refinement for Fe-o-TMAOTf5•2H2O.
  • Table S7. Atomic coordinates (×104) and equivalent isotropic displacement parameters (Å2 × 103) for Fe-o-TMAOTf5•2H2O.
  • Table S8. Bond lengths (Å) and angles (°) for Fe-o-TMAOTf5•2H2O.
  • Table S9. Anisotropic displacement parameters (Å2 × 103) for Fe-o-TMAOTf5•2H2O.
  • Table S10. Hydrogen coordinates (×104) and isotropic displacement parameters (Å2 × 103) for Fe-o-TMAOTf5•2H2O.
  • Table S11. Torsion angles (°) for Fe-o-TMAOTf5•2H2O.
  • References (2541)

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