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Synthesis and Electrochemical and Photophysical Studies of Tetrathiafulvalene-Annulated Phthalocyanines

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journal contribution
posted on 24.06.2005, 00:00 by Claudia Loosli, Chunyang Jia, Shi-Xia Liu, Marco Haas, Marylène Dias, Eric Levillain, Antonia Neels, Gael Labat, Andreas Hauser, Silvio Decurtins
The synthesis of tetrakis(tetrathiafulvalene)-annulated metal-free and metallophthalocyanines 58 via the tetramerization of the phthalonitrile derivative 4 is reported. All of them have been fully characterized by electronic absorption spectroscopy, thin-layer cyclic voltammetry, mass spectrometry, and elemental analysis. Their solution electrochemical data show two reversible four-electron oxidation waves, indicating that these fused systems are strong π-electron donors, which give rise to tetra- or octaradical cation species. For the metal-free phthalocyanine 5, additionally a reversible one-electron wave was found in the negative direction arising from the reduction of the macrocycle. Moreover, the tetrathiafulvalene unit acts as an efficient reductive electron-transfer quencher for the phthalocyanine emission, but upon its oxidation, an intense luminescence is switched on.