Synthesis And Properties Of Novel Norphthalocyanines Containing Thiacrown Ether-linked Tetrathiafulvalene Moieties

The porphyrazine and phthalocyanine derivative compounds, due to stability of the high heat, light, acid and alkali corrosion resistance, tightly condensed ring structure,delocalized conjugate π-electron system and excellent intramolecular and intermolecular charge transfer function, are paid attention to by the people day by day. Up to now, a great variety of symmetrical phthalocyanines have been extensively studied. However, there has been rarely reported on norphthalocyanines mainly because of much more difficult to synthesize and separate. Recently, there is much more increasing interest on the properties of the norphthalocyanines because of wide application in L-B film,electron-transporting materials, nonlinear optical materials, etc.Firstly, herein we have introduced the research status and development of phthalocyanines, tetrathiafulvalene, TTF-phthalocyanine and TTF-porphyrazine are summarized respectively. The compounds 12,13 were synthesized through metal template cyclization reaction. A Mg(II) template cyclization of the precurso with excess phthalonitrile gave the unsymmetrieal magnesium phthalocyanine. Its structure can be characterized by means of 1H-NMR, 13C-NMR, MALDI-TOF-MS, IR spectrum etc.Electrochemical investigations showed two quasi-reversible one-electron oxidation waves,one irreversible one-electron oxidation wave and two irreversible one-electron reduction waves, indicating that these compounds are good π-electron donors. Compound 12 reacted with 2,3,5,6-tetrafluoro-7,7,8,8-tetra-cyanoquinodimethane(F4TCNQ) to form a charge transfer complex that exhibited absorption bands in the vicinty of 750 and 960 nm.Compound 12 showed evident intramolecular charge transfer interactions in ground states and these may be explained on the basis of density functional theory and EPR. Compound13 showed similar characteristics.