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Tetrakis(trimethysilyl)phthalocyaninatoruthenium(II) (5) has been synthesized via the biaxially coordinated (( CH 3)3 Si )4 PcRu (3- Clpy )2 (2) complex by thermal decomposition of the axial ligands of 2. (( CH 3)3 Si )4 PcRu (5) was characterized by NMR, IR and UV-vis spectroscopy and elemental analysis. The trisubstituted (( CH 3)3 Si )3 PcRu (3- Clpy )2 (3) and disubstituted (( CH 3)3 Si )2 PcRu (3- Clpy )2 (4) complexes, formed as side products during the thermolysis of 2, could be isolated and characterized.

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The synthesis of a new Diels-Alder adduct 7 of [60Jtullerene and a phthalocyaninenickel compound containing a longer spacer than the originally reported Diels-Alder adduct 1 is described. The bisenophilic hemiporphyrazinenickel compound 11 reacts with [60]fullerene to form a Diels-Alder adduct 12 containing two fullerene units. Spectroelectrochemi-cal investigations of 7 and 12 reveal multiple reductions, which are attributed to the corresponding subunits of the molecules. In contrast to 1, the electron acceptor properties of the [60]fullerene unit in both molecules have no influence on the electronic properties of the phthalocyanine and hemiporphyrazine, respectively.Recently. we reported on the synthesis and the electrochemistry of the [60]fullerene derivative 1 which contains a covalently bound phthalocyanine"] ( Figure 1). In this green fullerene the two electroactive species are held in closc proximity by a spacer consisting of two six-membered rings. Multiple electron reductions of both electroactive moieties were determined and could be attributed to the corresponding subunits of the molecule. Athough a charge transfer from the phthalocyanine to the fullerene moiety at ambient conditions was not found we have shown that the optical properties of the phthalocyanine substructure of this molecule are characteristically influenced by the fullerene addend, especially after the first reduction of the CbO moiety. Figure 1. Diels-Alder adduct l [ l l of [bO]fullerene with an unsymmetrically substituted phthalocyaninenickel moietyIn this paper we report on the synthesis and electrochemical characterization of a new fullerene-phthalocyanine diad 7 and for the first time on a triad 12 contaming two fullerenes and a bridging hemiporphyrazine as macrocycle. The construction principle, which we used in thic approach is based on the pronounced dienophilic behaviour of [bO]fullerene undergoing facile Diels-Alder-reactions with a large variety of dienes. Hence, the synthesis of compounds 7 and 12 was accomplished by allowing [60]fullerene to react with thc correcponding macrocycles 6 and 11 containing one or two diene subunits, respectively (Scheme 1 and 2).The unsymetrically substituted phthalocyaninenickel compound 4 was synthesized using a statistical methodL2I. Three equivalents of 3,6-diheptylphthalodinitrile ['] (2) and one equivalent of 6,7-dicyano-1,4-dihydro-1,4-epoxynaph-thalene141 (3) were allowed to react with nickel acetate in the presence of a catalytic amount of DBU in pentanol under reflux (Scheme 1). The phthalocyaninenickcl compound 4 was separated from other phthalocyanines by column chromatography on silica gel with toluene and then chloroformlethanol as the mobile phases. Addition of the "tetraene" 5isl to the dienophilic phthalocyanine 4 in toluene at 110°C led to the formation of phthalocyanine 6 which was purified by column chromatography on dica gel with chloroform as eluentr2]. In Lhe 'H-NMR spectrum of compound 6 the signal of the 0-CH prolons appear as a singlet at 6 = 5.41. Due to the missing ...

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