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Issue 34, 2017
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Determinants of the efficiency of photon upconversion by triplet–triplet annihilation in the solid state: zinc porphyrin derivatives in PVA

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Abstract

Spectroscopic, photophysical and computational studies designed to expose and explain the differences in the efficiencies of non-coherent photon upconversion (NCPU) by triplet–triplet annihilation (TTA) have been carried out for a new series of alkyl-substituted diphenyl and tetraphenyl zinc porphyrins, both in fluid solution and in solid films. Systematic variations in the alkyl-substitution of the phenyl groups in both the di- and tetraphenyl porphyrins introduces small, but well-understood changes in their spectroscopic and photophysical properties and in their TTA efficiencies. In degassed toluene solution TTA occurs for all derivatives and produces the fluorescent S2 product states in all cases. In PVA matrices, however, none of the di-phenylporphyrins exhibit measurable NCPU whereas all the tetraphenyl-substituted compounds remain upconversion-active. In PVA the NCPU efficiencies of the zinc tetraphenylporphyrins vary significantly with their steric characteristics; the most sterically crowded tetraphenyl derivative exhibits the greatest efficiency. DFT-D computations have been undertaken and help reveal the sources of these differences.

Graphical abstract: Determinants of the efficiency of photon upconversion by triplet–triplet annihilation in the solid state: zinc porphyrin derivatives in PVA

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Publication details

The article was received on 14 Jul 2017, accepted on 14 Aug 2017 and first published on 15 Aug 2017


Article type: Paper
DOI: 10.1039/C7CP04746K
Citation: Phys. Chem. Chem. Phys., 2017,19, 23471-23482
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    Determinants of the efficiency of photon upconversion by triplet–triplet annihilation in the solid state: zinc porphyrin derivatives in PVA

    R. Rautela, N. K. Joshi, S. Novakovic, W. W. H. Wong, J. M. White, K. P. Ghiggino, M. F. Paige and R. P. Steer, Phys. Chem. Chem. Phys., 2017, 19, 23471
    DOI: 10.1039/C7CP04746K

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