Synthesis Of ABAB Type Phthalocyanines By "Cross Condensation" Method And Study On Their Spectra

Synthesis and study on the "incoordinate"substituted phthalocyanies are valuable both in theoretic study and potential application of phthalocyanines. Attentions to these complexes are attracted in many fields like, for example, nonlinear optical materials, photoconducting device, molecular rectifier, photo dynamic therapy, and LB film fabrication. As listed below, nine ABAB type phthalocyanines were synthesized by the "cross condensation"method, where A and B are different isoindole units. 1,15(or 1,18)-bis -(2',2',4'-trimethyl-3'-pentoxy)phthalocyanine (IV-1); 1,15(or 1,18)-bis-(2',2',4'-trimethyl-3'-pentoxy)phthalocyaninatocopper (IV-2); 1,15(or 1,18)-bis -(2',2',4'-trimethyl-3'-pentoxy)phthalocyaninatocobalt (IV-3); 1,15(or 1,18)-bis -(2',4'-ditertbutylphenoxy)phthalocyanine (IV-4); 1,15(or 1,18)-bis-(2',4'-ditertbutylphenoxy)phthalocyaninatocopper (IV-5); 1,15(or 1,18)-bis-(2',4'-ditertbutylphenoxy)phthalocyaninatocobalt (IV-6); 1,4,15,18-tetraisopropyloxyphthalocyanine (IV-7); 1,4,15,18-tetraisopropyloxyphthalocyaninatocopper (IV-8); 1,4,15,18-tetraisopropyloxyphthalocyaninatocobalt (IV-9)。The IR, UV/Vis, fluorescence spectra, MS, 1HNMR, and element analysis on some of these complexes were carried out. By comparing the UV/Vis spectra of IV-1 and V, the　λmax and split of Q band were mainly related to the number of substituents and the polarity of solvents. The results showed that, the UV/Vis spectra were merely influenced by the concentration of solutions of different solvents for about only 1~2nm shift of Q band. Comparing to V, the B band of IV-1 red shift about 14nm, and the blue shift of Q band was about 14~20nm; additionally, the split of Q band of metal free ones were induced by the increase of solvent polarity what means the influence of solvent polarity is different on the two bands, Q1 and Q2, of split Q band. The 1~HNMR spectra obeyed the rule of aromatic system . The chemical shift of center H is low and that of the H on the outer ring is high where the shift of H at αand βpositions of benzene ring were also different. The mix condensation of 3,6-diisobutoxyphthalonitrile and none substituted phthalonitrile was also attempted. The block substituents led to a result that, determined by MS, the composition of product was different from that of phthalonitriles bearing substituents not so large. And because AB3 type phthalocyanine was detected, the AABB type was also present conjecturally. This result is also different from that of mix condensation of 3,6-diphenylphthalonitrile and none substituted phthalonitrile reported in literature.