Novel peripherally tetra-substituted octacationic metal-free and metallophthalocyanines: Synthesis, spectroscopic characterization and aggregation behaviours

摘要

In this study, new l,3-bis[3-(diethylamino)phenoxy]propan-2-ol 1 and phthalonitrile derivative 3 bearing 1,3-bis[3-(diethylamino)phenoxy]propan-2-ol substituent at peripheral position have been synthesized. The synthesis, characterization of the tetra-4-(2-[3-(diethylamino)phenoxy]-l-{[3-(diethylamino)phenoxy]methyl}ethoxy) substituted metal-free 4 and metallophthalocyanines 5, 6, 7, (MPcs, M = Ni, Co, Cu) are reported for the first time. These new metal-free and metallophthalocyanines 4-7 were converted into water soluble quaternized products by the reaction with methyl iodide 4a-7a. The metal-free phthalocyanine 4 was prepared from phthalonitrile derivative 3 in n-pentanol with a catalytic amount of 1,8-diazabicyclo[5.4.0]undec-7ene (DBU). Metallophthalocyanines 5-7 were prepared by cyclotetramerization of 3 with the corresponding metal salts (NiCl_2, CoCl_2, CuCl_2) in n-pentanol with a catalytic amount of DBU. The aggregation behaviours of the phthalocyanine complexes were studied in different solvents and concentrations. The new compounds have been characterized by using UV-vis, IR,~1H NMR,~(13)C NMR, MS spectroscopic data and elemental analysis.