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Journal of the American Chemical Society
Volumn 130, Issue 38, 2008, Pages 12639-12641
Zeolite-like metal-organic frameworks as platforms for applications: On metalloporphyrin-based catalysts
Author keywords

[No Author keywords available]
Indexed keywords

CARBON DIOXIDE; CATION; CYCLOHEXANOL; CYCLOHEXANONE; METALLOPORPHYRIN; METHANOL; ORGANIC COMPOUND; SURFACTANT; ZEOLITE;
EID: 52449097755     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja804703w     Document Type: Article
Times cited : (580)
References (35)
  • 19
    • 52449127064 scopus 로고    scopus 로고
    • Comprehensive Supramolecular Chemistry; Suslick, K. S., Ed.; Supramolecular Reactivity and Transport: Bioinorganic Systems; Pergamon: Oxford, 1996; 5.
    • (d) Comprehensive Supramolecular Chemistry; Suslick, K. S., Ed.; Supramolecular Reactivity and Transport: Bioinorganic Systems; Pergamon: Oxford, 1996; Vol. 5.
  • 20
    • 0010730955 scopus 로고
    • Montanari, F, Casella, L. Eds, Kluwer: Dordrecht, The Netherlands
    • (e) Meunier, B. In Metalloporphyrin Catalyzed Oxidations; Montanari, F., Casella, L. Eds.; Kluwer: Dordrecht, The Netherlands, 1994; pp 1-48.
    • (1994) Metalloporphyrin Catalyzed Oxidations , pp. 1-48
    • Meunier, B.1
  • 33
    • 52449115536 scopus 로고    scopus 로고
    • All chemicals were Aldrich reagent grade and used as received, unless otherwise noted. In a 20 mL vial, a mixture of In(NO3) 3·xH2O (0.015 g, 0.0435 mmol, 4,5-H 3ImDC (0.014 g, 0.087 mmol, DMF (1 mL, CH3CN 1 mL, and 0.1 mL of 8 mM methanol solution of [H2TMPyP][p-tosyl] 4, were mixed; the vial was sealed and heated to 85°C for 12 h, then to 105°C for 24 h with a heating rate of 1.5°C/min, and then cooled down to room temperature with a cooling rate of 1°C/min. Dark red crystals of 1, H2TMPyP]4+ encapsulated inside rho-ZMOF, were then collected, washed with DMF, and then washed with methanol several times, until no residual amount of porphyrin was present in the washing solution, as evident from the UV-vis spectrum of the washing solution
    • 4+ encapsulated inside rho-ZMOF, were then collected, washed with DMF, and then washed with methanol several times, until no residual amount of porphyrin was present in the washing solution, as evident from the UV-vis spectrum of the washing solution.
  • 34
    • 52449126299 scopus 로고    scopus 로고
    • In an attempt to maximize porphyrin loading into rho-ZMOF, 1.198 mmole of 4,5-H3ImDC, 0.5 mmole of In(NO3) 3·xH2O, 30 μmol of [H2TMPyP, p-tosyl]4, DMF, and ethanol (3 mL each) were mixed in a 25 mL scintillation vial. The vial was then heated using the same procedure for the synthesis of 1. The resultant crystals, 1′, were washed several times with methanol until no residual porphyrin was present. A 10.8 mg portion of 1′ was dissolved in 25 mL of concd HNO3, from which 1 mL was diluted to the of 10 mL using DI water. Using atomic absorption to determine concentration of In3+ ions and UV-vis for porphyrin (ε438, 1.9 × 105 M-1 cm-1, an estimate of 67% loading of porphyrin into the α-cages (each made of 24 In3+ ions) was possible. Further increase of the free
    • 3+ ions) was possible. Further increase of the free-base porphyrin concentration in the reaction mixture precludes formation of crystalline material.
  • 35
    • 52449133871 scopus 로고    scopus 로고
    • 4, 100 μmol chlorobenzene as internal standard, 10 mL cyclohexane, and 88 mg of 1a (equivalent to 2.9 μmol of Mn-TMPyP) were mixed, under aerobic conditions, in a 25 mL round-bottom flask fitted with a silicone septum. The reaction mixture was then held at 65°C in an isothermal bath for the required amount of time, as determined by analyzing aliquots of the mixture over time using GC-FID.
    • 4, 100 μmol chlorobenzene as internal standard, 10 mL cyclohexane, and 88 mg of 1a (equivalent to 2.9 μmol of Mn-TMPyP) were mixed, under aerobic conditions, in a 25 mL round-bottom flask fitted with a silicone septum. The reaction mixture was then held at 65°C in an isothermal bath for the required amount of time, as determined by analyzing aliquots of the mixture over time using GC-FID.

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