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XIX

, 2530 2011 .

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PHOTOCHEMICAL UPCONVERSION

OF VISIBLE AND NIR LIGHT

Fckel B.,a Clady R.G.C.R.,a Roberts D.A.,a Tayebjee M.J.Y.,a Ekins-Daukes N.J.,b Schmidt T.W.a NSW 2006, Australia: m.crossley@chem.usyd.edu.au Department of Physics and the Grantham Institute for Climate Change, Upconversion (UC) is the process whereby a stream of light of a given photon energy is converted into one of a higher energy. Photochemical UC occurs where emitter triplet states are produced through triplet energy transfer from sensitizer molecules excited with low energy photons. The triplet emitter molecules undergo TT annihilation to yield excited singlet states which emit upconverted fluorescence. Pd(II) tetrakisquinoxalinoporphyrin 2, synthesized from porphyrin 1, is a very efficient sensitizer molecule for the UC process.

By using 2 as sensitizer and rubrene as the emitter, red to yellow UC occurs with TTA efficiency far in excess of the statistical 11.1% limit of singlet formation. More than 60% of the triplet molecules that decay by TTA produce emitters in their first excited singlet state, so that the observed TTA efficiency exceeds 40% at the point of the highest triplet emitter concentration. This result disproves any spin-statistical limitation for the annihilation efficiency.

Using 2 and perylene we obtain a new record for the peak-to-peak TTAUC energy margin of 0.94 eV. Red to green, and green to blue light UC is observed using other emitters.

We also report photochemical UC of NIR light to the visible spectrum mediated by molecular oxygen. Thereby, we address two of the main challenges in the field of photochemical UC, (i) UC of photons above 800 nm and (ii) utilization of molecular oxygen, which is necessarily excluded in conventional photochemical UC systems.

12

RELATIONSHIP BETWEEN THE MOLECULAR STRUCTURES

AND SPECTROSCOPIC AND ELECTROCHEMICAL PROPERTIES

OF PORPHYRINOIDS



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