Antimony(+5) insertion induces both electron-rich and electron-poor parts within the porphyrin structure resulting in a push–pull style intramolecular charge transfer.
Photodynamics of an aluminum(iii) porphyrin-phosphorous(v) porphyrin heterodimer reveals initial formation of a singlet CT state which relaxes to a high-energy triplet CT state lasting for about 105 μs.
A high-potential
supramolecular triad (TPE-AlPor ← Im-C60) composed
of aluminum(III) porphyrin (AlPor), fullerene
(C60), and tetraphenylethylene (TPE) has been constructed.
The fullerene and tetraphenylethylene units are bound axially to opposite
faces of the porphyrin plane via coordination and covalent bonds,
respectively. The ground and excited-state properties of the triad
and reference dyads are studied using steady-state and time-resolved
spectroscopic techniques. The transient data show that photoexcitation
results in charge separation from tetraphenylethylene to the excited
singlet state of the porphyrin (1AlPor*), generating a
high-energy (2.14 eV) charge-separated state, (TPE)•+-(AlPor)•–, in toluene. A subsequent electron
migration from the AlPor–• to fullerene generates
a second high-energy (1.78 eV) charge-separated state (TPE)•+-AlPor ← Im-(C60)•–. The
lifetime of the charge separation is about 25 ns. The high energy
stored in the form of charge-separated states along with their reasonable
lifetimes makes these donor–acceptor systems potential electron-transporting
catalysts to carry out energy-demanding photochemical reactions, especially
in artificial photosynthesis for conversion of solar energy into chemical
energy.
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