Novel Homo- and Heterodimetallic Heterobinuclear Phthalocyaninato-Triazolehemiporphyrazinate Complexes Gema de la Torre, † M. Victoria Martı ´nez-Dı ´az, † Peter R. Ashton, ‡ and Toma ´ s Torres* ,† Departamento de Quı ´mica Orga ´ nica (C-I), Universidad Auto ´ noma de Madrid, E-28049 Madrid, Spain, and School of Chemistry, University of Birmingham, Edgbaston, B15 2TT Birmingham, United Kingdom Received June 11, 1998 A family of unsymmetrical heterobinuclear phthalocyaninato-triazolehemiporphyrazinate (Pc-Thp) complexes 2a-e has been synthesized for the first time by statistical mixed condensation of regioisomerically pure dicyanotriazolehemiporphyrazinates 5a,b with differently substituted phthalonitrile derivatives 6 and 7. This stepwise approach allows to prepare heterodimetallic complexes 2b and 2d incorporating Ni(II) or Zn(II) in the cavity of each macrocyclic unit as well as a “push-pull” homodimetallic Pc-Thp compound, 2e, bearing acceptor (SO 2 C 8 H 17 ) and donor (OC 8 H 17 ) substituents. The UV-vis spectra of compounds 2a-e in CHCl 3 exhibit a broad and split Q-band indicative of intra- and intermolecular interactions. Moreover, a strong red-shifting (25-50 nm) relative to the octasubstituted mononuclear Pc compounds is observed, which is in agreement with the enlargement of the π-conjugated Pc system. Interestingly, the optical behavior of Pc-Thp compounds 2a-d is driven by the central metal included into the Pc moiety. Compound 2e exhibits a low degree of intermolecular interactions in solution taking into account its UV-vis and 1 H NMR spectra. Introduction The aggregation of phthalocyanines 1-3 (Pcs) has been extensively studied to elucidate how these molecules interact intermolecularly in solution. These studies have shown that the coupling between electronic states of two or several Pcs leads to important changes in the absorp- tion spectra of these compounds, namely a decrease in the intensity of the Q-band which is at the same time blue-shifted. However, very few examples of intramo- lecular interactions between Pc units have been studied in homodimetallic binuclear phthalocyanine systems in which the Pc units have been connected through π-con- jugated condensed systems such as benzene 4 or naph- thalene 5 rings. Other relevant examples of Pc dimeric systems are the homodimetallic ethynyl- or butadiynyl- bridged bisphthalocyanines described by others 6 and us. 7 In all these cases, the Q-band undergoes a shift to the near-IR region, which has been attributed to the enlarge- ment of the π-conjugated system, with concomitant splitting of the Q-band as a consequence of intramolecu- lar electron coupling between the Pc units. The same strong red-shifting of the Q-band has been observed in mononuclear phthalocyanines in which the π-system has been extended by annelation with other benzene units 8 and to a lesser extent by introduction of π-conjugated substituents. 9 Much less effort has been focused on the preparation of heterodimetallic 7 or heterobinuclear 10 Pc systems. 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