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High-Potential Hypervalent Antimony(V) Porphyrin-C60 Conjugates: Excitation Energy Transfer Dominates over Reductive

Niloofar Zarrabi1, Jatan K Sharma2, Katya Andzelevich1

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Novel antimony(V) porphyrin-fullerene conjugates were synthesized. Ultrafast energy transfer from the porphyrin to the fullerene unit was observed, with direct energy transfer being the dominant process.

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Area of Science:

  • Supramolecular Chemistry
  • Photochemistry
  • Materials Science

Background:

  • Hypervalent antimony(V) porphyrins possess high redox potentials.
  • Fullerenes, like C60, are well-established electron acceptors.
  • Porphyrin-fullerene conjugates are studied for energy and electron transfer processes.

Purpose of the Study:

  • To synthesize and characterize novel antimony(V) porphyrin-fullerene conjugates (SbP-C60 and SbPF3-C60).
  • To investigate the excited state energy patterns and energy transfer mechanisms in these dyads.
  • To explore the potential for unusual energy landscapes due to high redox potentials of antimony(V) porphyrins.

Main Methods:

  • Covalent linkage of antimony(V) porphyrins with C60.
  • Synthesis of SbP-C60 and SbPF3-C60 conjugates.
  • Time-resolved spectral analysis to study energy transfer dynamics.

Main Results:

  • Formation of antimony(V) porphyrin-fullerene conjugates.
  • Observation of ultrafast singlet-singlet energy transfer from porphyrin to C60.
  • Energetics suggest Förster mechanism or electron transfer followed by recombination are possible pathways.
  • Experimental data indicate direct energy transfer is the dominant process.

Conclusions:

  • Antimony(V) porphyrin-fullerene conjugates exhibit efficient ultrafast energy transfer.
  • Direct energy transfer, likely via the Förster mechanism, dominates over charge separation.
  • These novel dyads offer a unique platform for studying energy transfer in tailored molecular systems.