A Binuclear Phthalocyanine Containing Two Different Metals

Abstract

The unsymmetrical binuclear phthalocyanine 4a and the symmetrical binuclear phthalocyanine 4b with two different metals (Ni and Cu), as well as the correspondent binuclear phthalocyanines with two Ni atoms (4c and 4d) were synthesized from the benzoannulated dicyano-substituted Ni phthalocyanine 2. Atomic absorption spectroscopy verified unambiguously the presence of Ni and Cu in the binuclear

Reactivity of Dehydrometallophthalocyanines and ‐porphyrazines

“…Thus, in Et 2 O the amount of Pb-A C H T U N G T R E N N U N G (OAc) 4 cannot exceed one equivalent, otherwise in addition to the oxidation of the aminotriazole moiety in 1, an oxidation of the macrocycle takes place. Moreover, if weakly or non-coordinating solvents, such as halomethanes, toluene, benzene, and so forth, are used, oxidation of the macrocycle competes noticeably with the desired aminotriazole oxidation.…”

“…Moreover, if weakly or non-coordinating solvents, such as halomethanes, toluene, benzene, and so forth, are used, oxidation of the macrocycle competes noticeably with the desired aminotriazole oxidation. Coordinating solvents of N-basic nature, for example, pyridine and amines, could also not be applied, because they either drastically decrease the oxidizing potential of Pb-A C H T U N G T R E N N U N G (OAc) 4 or undergo a reaction with this oxidant, so that no generation of dehydro-PcZn 2 from PcZn 1 was observed even in the presence of excess PbA C H T U N G T R E N N U N G (OAc) 4 .…”

“…[3] The corresponding dimer formed from 2 is expected to exhibit interesting optical and electronic properties. [4] If 2 is generated in diethyl ether in the same manner as described in our previous work (a saturated solution of Pb- 4 in acetic acid was utilized to oxidize 1), [2] but in absence of dienes, only a mixture of ethyloxy-(3) and the acetoxy-(4) derivatives (see Scheme 1) is formed in good yield. Although 3 and 4 could not be separated by column chromatography, both were clearly identified using MALDI-TOF and 1 H and 13 C NMR spectroscopy (see Supporting Information).…”

“…The zinc dehydrophthalocyanine 2 and zinc dehydrobenzoporhyrazine 8 a were generated from the 1N-aminobenzotriazole-annulated zinc phtalocyanine 1 and zinc benzoporhy-A C H T U N G T R E N N U N G razine 8, respectively, by oxidation with PbA C H T U N G T R E N N U N G (OAc) 4 in different solvents, for example, diethyl ether, tetrahydrofuran, acetic acid, and benzene. The reactivity of 2 and 8 a was studied in detail.…”

“…By using diethyl ether as a solvent and excess of the mentioned dienes, the corresponding Diels-Alder cycloaddition products of dehydro-PcZn 2 were formed in 50-60 % yield. [2] In the following we report about more detailed investigations concerning the reactivity of zinc dehydrophthalocyanine 2 and zinc dehydrobenzoporphyrazine 8 a, generated from the corresponding 1N-aminotriazole-annulated macrocycles 1 (see Scheme 1) and 8, respectively (see Scheme 2, later) upon oxidation with PbA C H T U N G T R E N N U N G (OAc) 4 under different conditions.…”