Science Advances

Supplementary Materials

This PDF file includes:

  • Section S1. Materials and methods
  • Fig. S1. Calibration distance for 2D ROESY NMR.
  • Fig. S2. Octahedral nanocage.
  • Fig. S3. 1H NMR spectrum of a synthesized Pd6L412+ nanocage in D2O.
  • Fig. S4. 13C NMR spectrum of a synthesized Pd6L412+ nanocage.
  • Fig. S5. Visible charge transfer complex of 9-MA.
  • Fig. S6. Host-guest complexation and NMR upfield shifts.
  • Fig. S7. Temperature dependence of population heterogeneity of caged 9-MA.
  • Fig. S8. Charge transfer complex with 1-MeNap.
  • Fig. S9. Host-guest complexation of 1-MeNap.
  • Fig. S10. Temperature-dependent 1H NMR of methyl protons.
  • Fig. S11. Complexation of Tol and nanocage.
  • Fig. S12. 13C NMR spectrum of Tol ⊂ Cage.
  • Fig. S13. Optimized structure of Tol inside a nanocage.
  • Fig. S14. Substituent-dependent steady-state absorption of host-guest CT complexes of Tol derivatives.
  • Fig. S15. Formation of ortho-xylene ⊂ Cage complex.
  • Fig. S16. 2D ROESY spectrum of ortho-xylene ⊂ Cage complex in D2O in 800 MHz.
  • Fig. S17. Formation of para-xylene ⊂ Cage complex.
  • Fig. S18. ROESY spectrum of para-xylene ⊂ Cage complex in D2O (800 MHz).
  • Fig. S19. Formation of meta-xylene ⊂ Cage complex.
  • Fig. S20. 1H-1H 2D ROESY NMR spectrum of meta-xylene ⊂ Cage complex in D2O in 800 MHz.
  • Fig. S21. Complexation of para-OMeTol with nanocage.
  • Fig. S22. 2D 1H-1H ROESY NMR spectrum of para-OMeTol ⊂ Cage complex in D2O.
  • Fig. S23. Complexation of para-FluoroTol with nanocage.
  • Fig. S24. 2D 1H-1H ROESY NMR spectrum of para-FluoroTol ⊂ Cage complex in D2O (800 MHz).
  • Fig. S25. Electronics- and regioisomerism-dependent molecular packing of Tol derivatives inside the nanocage.
  • Fig. S26. 1H NMR spectra of Tol ⊂ Bipycage (top) in D2O and its comparison with Tol ⊂ Encage in D2O.
  • Fig. S27. 2D 1H-1H ROESY NMR spectrum of Tol ⊂ Bipycage complex in D2O (800 MHz).
  • Fig. S28. Transient absorption of radical cation of 9-MA ⊂ Cage and corresponding decay.
  • Fig. S29. PCET reaction for 9-MA ⊂ Cage complex.
  • Fig. S30. Substrate isotope dependence on C─H vs. C─D bond cleavage and primary KIE.
  • Fig. S31. C─H versus C─D bond cleavage and primary KIE.
  • Fig. S32. Tol radical cation decay inside the nanocage.
  • Fig. S33. Excited-state absorption of coupled host-guest CT state.
  • Fig. S34. Solvation relaxation of the excited host-guest CT state.
  • Fig. S35. Photoreaction on encapsulated 9-MA, illuminated by cheap green LED (530 nm).
  • Fig. S36. Rate of photoreaction is dependent on O2 concentration.
  • Fig. S37. Photooxidized product identification.
  • Fig. S38. Both benzylic and ring oxidation take place for 9-MA.
  • Fig. S39. Photoreaction under high O2 pressure for 30 min.
  • Fig. S40. UV light–mediated photoreaction under ambient O2.
  • Fig. S41. Photocatalysis on caged 9-MA.
  • Fig. S42. Control photoreactions for mechanism elucidation.
  • Fig. S43. Selective photooxidation products of 1-MeNap.
  • Fig. S44. Spectral characteristics of the photoproducts.
  • Fig. S45. Mass spectrum of photooxidation product, benzaldehyde.
  • Fig. S46. Concomitant decay of the substrate and rise of the oxidized product with a lag phase.
  • Fig. S47. Benzyl alcohol to benzaldehyde formation.
  • Fig. S48. Photooxidation of secondary benzylic radicals.
  • Fig. S49. Photoreactivity of cage incarcerated tertiary benzylic radicals under O2.
  • Fig. S50. Photooxidation of para-xylene inside the nanocage.
  • Fig. S51. Ortho-xylene oxidation by light.
  • Fig. S52. Photocatalytic oxidation of meta-xylene.
  • Fig. S53. Oxidation of para-OMeTol with blue light.
  • Fig. S54. Electron-withdrawing substituent effect on photocatalytic oxidation of para-FluoroTol.
  • Fig. S55. Photocatalytic oxidation rates are strongly dependent on molecular packing of the substrates inside the cage.
  • Fig. S56. Cage electronics perturb the photocatalytic reaction rates.
  • Fig. S57. Cage behavior like a prototypical photoenzyme: Tuning photoproduct selectivity by changing the cage electronics.
  • Fig. S58. Parallel E-field and C─H Raman stretches.
  • Fig. S59. Antiparallel E-field effects on C─H Raman stretches.
  • Fig. S60. E-field effects on C─H bond lengths.
  • Fig. S61. Effects of aromaticity on E-field induced C─H bond polarization.
  • Scheme S1. Making of the nanocage.
  • Scheme S2. Plausible mechanism for photooxidation of 9-MA inside cage.
  • Scheme S3. Oxidation of 1-MeNap by light.
  • Table S1. Comparison between 2D NMR and molecular modeling–obtained relative distances.
  • Table S2. Geometric separation of Tol methyl protons from the triazine walls for different derivatives.
  • References (6972)

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