Additional material for this item is available at http://advances.sciencemag.org/cgi/content/full/6/11/eaaz3318/DC1

Section S1. Spectroscopic characterization of 1

Article S2. Voltammetry of 1

Article S3. UV-vis spectroscopy 1 + variable buffers

Article S4. Homoconjugation

Article S5. Kinetic analysis

Article S6. Efficient determination of overvoltage

Article S7. Selectivity for H2O against H2O2

Article S8. Conceptual background for E1/2 and PKa scaling relationships

Article S9. Monocrystalline X-ray structure

Figure S1. Full high resolution ESI mass spectrum of 1 with peaks identified, as labeled.

Figure S2. High resolution ESI mass spectrum and isotope fits for the [M5+ + 3OTf] ion.

Figure S3. UV-vis spectrum 1 in NOT,NOT′ -Dimethylformamide.

Figure S4. IR spectrum of 1.

Figure S5. A CV of an Ar-sparged solution from 1.

Figure S6. Fe sweep rate surveyIII/ FeII redox couple of 1 in unbuffered solution.

Figure S7. Voltammograms of an Ar bubbling solution of 1 before and after addition of buffered AcOH.

Figure S8. Fe investigationIII/ FeII redox couple of 1 with AcOH buffer titrations.

Figure S9. Fe sweep rate surveyIII/ FeII redox couple 1 in AcOH buffered solution.

Figure S10. Fe investigationIII/ FeII redox couple of 1 with BzOH buffer titrations.

Figure S11. Fe sweep rate surveyIII/ FeII redox couple of 1 in BzOH buffered solution.

Figure S12. Fe investigationIII/ FeII redox couple of 1 with SalOH buffer titrations.

Figure S13. Fe sweep rate surveyIII/ FeII redox couple 1 in SalOH buffered solution.

Figure S14. Fe investigationIII/ FeII redox couple 1 with TFA buffer assays.

Figure S15. Fe sweep rate surveyIII/ FeII redox couple 1 in TFA buffered solution.

Figure S16. Fe investigationIII/ FeII redox couple of 1 with titrations of [DMF-H]OTf buffer.

Figure S17. Fe investigationIII/ FeII redox couple 1 with titrations of [Lut-H]BF4 amortize.

Figure S18. Changes in E1/2(FeIII/ FeII) with varying buffers (and concentrations).

Figure S19. CV of an O2-Sprayed MeCN solution containing 100 mM [AcOH] buffer before (black) and after (blue) addition of 30 M 1.

Figure S20. Voltammograms of 1 with AcOH buffer under various solution conditions.

Figure S21. Voltammograms of 1 with BzOH buffer under various solution conditions.

Figure S22. Voltammograms of 1 with SalOH buffer under various solution conditions.

Fig. S23. Voltammograms of 1 with TFA buffer under various solution conditions.

Figure S24. Voltammograms of 1 with [Lut-H+] buffer under various solution conditions.

Figure S25. Voltammograms of 1 with [DMF-H]OTf buffer under various solution conditions.

Figure S26. Rinse the assays for all buffers used in this study.

Figure S27. UV-vis spectra of MeCN solutions containing 1 (~ 0.05 mm), [n-Bu4N][BF4] (~ 0.05 M) and various 1: 1 buffers (~ 0.05 M, as identified).

Figure S28. Wave foot analysis for the buffer concentrations used in this study (all at 1 atm O2).

Figure S29. Wave foot analysis for all partial pressure O2 measurements performed in this study (all at 20 mM buffer).

Figure S30. TOFmax vs [substrate] plots for the buffers used in this study.

Figure S31. Land of kobs with respect to the partial pressure of O2 for each of the buffers used in this study.

Figure S32. RRDE analysis using ferrocene to estimate collection efficiency.

Figure S33. RRDE analysis for ORR catalyzed by 1 using [DMF-H]OTf buffer.

Figure S34. RRDE analysis for ORR catalyzed by 1 using TFAH buffer.

Figure S35. RRDE analysis for ORR catalyzed by 1 using the SalOH buffer.

Figure S36. RRDE analysis for ORR catalyzed by 1 and BzOH buffer.

Figure S37. RRDE analysis for ORR catalyzed by 1 and AcOH buffer.

Figure S38. The complete radiographic model of [Fe-o-TMA]OTf5• 2H2O depicted with balls and sticks.

Figure S39. The complete numbering scheme of the cation-only part of [Fe-o-TMA]OTf5• 2H2O with thermal ellipsoid probability levels of 50%.

Figure S40. The radiographic model of the cation-only part of [Fe-o-TMA]OTf5• 2H2O from a secondary point of view showing the structural isomer of porphyrin.

Figure S41. The complete numbering of the disordered triflate at a general position in the model of [Fe-o-TMA]OTf5• 2H2O with thermal ellipsoid probability levels of 50%.

Figure S42. The unit cell of [Fe-o-TMA]OTf5• 2H2O, with a surface that represents a level of 1.5 e / Å3.

Figure S43. All orientations of the disordered triflate are shown relative to the

4¯

axis of rotation, represented by red lines.

Table S1. Summary of E1/2(FeIII/ FeII) (V) against 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-Bu4N][BF4] and ~ 0.05 M buffer.

Table S3. Homoconjugation formation constants for the buffers used in this study.

Table S4. Values ​​calculated for non-homoconjugated acid and conjugated base ([HA]free = [A]free and [HB+]free = [B]free) for different identities and buffer concentrations.

Table S5. Average percentage H2O2 trained for 1-ORR catalyzed in MeCN containing various buffers.

Table S6. Refinement of data and Crystal structure for [Fe-o-TMA]OTf5• 2H2O.

Table S7. Atomic coordinates (× 104) and equivalent isotropic displacement parameters (Å2 × 103) for [Fe-o-TMA]OTf5• 2H2O.

Table S8. Connection lengths (Å) and angles (°) for [Fe-o-TMA]OTf5• 2H2O.

Table S9. Anisotropic displacement parameters (Å2 × 103) for [Fe-o-TMA]OTf5• 2H2O.

Table S10. Hydrogen coordinates (× 104) and the isotropic displacement parameters (Å2 × 103) for [Fe-o-TMA]OTf5• 2H2O.

Table S11. Torsion angles (°) for [Fe-o-TMA]OTf5• 2H2O.

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