Synthesis and electrochemical and photophysical studies of tetrathiafulvalene-annulated phthalocyanines.
The synthesis of tetrakis(tetrathiafulvalene)-annulated metal-free and metallophthalocyanines 5-8 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 pi-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.
Loosli
Claudia
C
Departement für Chemie und Biochemie, Universität Bern, Freiestrasse 3, 3012 Bern, Switzerland.
Jia
Chunyang
C
Liu
Shi-Xia
SX
Haas
Marco
M
Dias
Marylène
M
Levillain
Eric
E
Neels
Antonia
A
Labat
Gael
G
Hauser
Andreas
A
Decurtins
Silvio
S