Fixed distance photoinduced electron transfer between Fe and Zn porphyrins encapsulated within the Zn HKUST-1 metal organic framework

Dalton Trans. 2015 Feb 21;44(7):2959-63. doi: 10.1039/c4dt02685c.

Abstract

An attractive strategy for the development of photocatalytic metal organic framework (MOF) materials is to co-encapsulate a photoactive electron donor with a catalytic electron acceptor within the MOF. Here we report the co-encapsulation of both Zn(ii) tetrakis(tetra 4-sulphonatophenyl)porphyrin (Zn4SP) and Fe(iii) tetrakis(tetra 4-sulphonatophenyl)porphyrin (Fe4SP) into an HKUST-1 (Zn) MOF and demonstrate photoinduced electron transfer (ET) between the co-encapsulated guest. Photo-excitation of the Zn4SP results in fixed-distance inter-molecular ET between the encapsulated (3)Zn4SP and the Fe(iii)4SP as evident by the reduction in the encapsulated (3)Zn4SP lifetime from 890 μs (kobs = 1.1 × 10(3) s(-1)) to 83 μs (kobs = 1.2 × 10(4) s(-1)) in the presence of Fe4SP giving a kET ∼ 1.1 × 10(4) s(-1). The data are consistent with ET taking place between encapsulated porphyrins that are two cages apart in distance with a reorganizational energy of ∼1.65 eV, β = 1.25 and ΔG° = -0.97 eV (within a semi-classical Marcus theory framework).

MeSH terms

  • Electron Transport / physiology
  • Iron / chemistry*
  • Iron / metabolism
  • Metal-Organic Frameworks
  • Organometallic Compounds / chemistry*
  • Organometallic Compounds / metabolism
  • Photic Stimulation* / methods
  • Porphyrins / chemistry*
  • Porphyrins / metabolism
  • Protein Structure, Secondary
  • Zinc / chemistry*
  • Zinc / metabolism

Substances

  • Metal-Organic Frameworks
  • Organometallic Compounds
  • Porphyrins
  • bis(1,3,5-benzenetricarboxylate)tricopper(II)
  • Iron
  • Zinc