An unsymmetric, peripherally octasubstituted phthalocyanine (Pc) 1, which contains a combination of dipyrido[3,2-f:2‘,3‘-h] quinoxaline and 3,5-di-tert-butylphenoxy substituents, has been obtained via a statistical condensation reaction of two corresponding phthalonitriles. Synthetic procedures for the selective metalation of the macrocyclic cavity and the periphery of 1 were developed, leading to the preparation of the key precursor metallophthalocyanines 3−5 in good yields. Two different strategies were applied to the synthesis of compact dyads MPc−Ru(II) 6−8 (M = Mg(II), Co(II), Zn(II)). Intramolecular electronic interactions in these dyads were studied by absorption, emission, and transient absorption spectroscopy. Upon photoexcitation, these dyads exhibit efficient intramolecular energy transfer from the Ru(II) chromophore to the MPc moiety.

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 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.